EP1492405A1 - Herbicidal composition comprising phenylpropynyloxypyridine compounds - Google Patents

Herbicidal composition comprising phenylpropynyloxypyridine compounds

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Publication number
EP1492405A1
EP1492405A1 EP03720414A EP03720414A EP1492405A1 EP 1492405 A1 EP1492405 A1 EP 1492405A1 EP 03720414 A EP03720414 A EP 03720414A EP 03720414 A EP03720414 A EP 03720414A EP 1492405 A1 EP1492405 A1 EP 1492405A1
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EP
European Patent Office
Prior art keywords
alkyl
hydrogen
substituted
poly
mono
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03720414A
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German (de)
French (fr)
Inventor
Jürgen Syngenta Crop Protection AG SCHAETZER
Jean Syngenta Crop Protection AG WENGER
Roger Graham Syngenta Crop Protection AG HALL
Kurt Syngenta Crop Protection AG NEBEL
Stephen Syngenta Crop Protection AG HOLE
André Syngenta Crop Protection AG STOLLER
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Syngenta Participations AG
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Syngenta Participations AG
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Publication of EP1492405A1 publication Critical patent/EP1492405A1/en
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

  • the present invention relates to a novel herbicidal composition
  • a novel herbicidal composition comprising a herbicidal active ingredient combination that is suitable for the selective control of weeds in crops of useful plants, for example in crops of cotton, soybeans, sugar beet, sugar cane, plantation crops, rape and, especially, cereals, rice and maize.
  • the invention relates also to a method of controlling weeds in crops of useful plants and to the use of the novel composition for that purpose.
  • variable amounts of active ingredients that is to say a compound of formula I together with one or more of the herbicidal active ingredients indicated below, which are known and some of which are also commercially available, exhibits a synergistic action that is capable of controlling, both pre- emergence and post-emergence, the majority of weeds occurring especially in crops of useful plants.
  • R 3 and R 4 together are C 2 -C 5 alkylene;
  • R 5 is hydrogen or d-C 8 alkyl;
  • R 6 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl; it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C 4 alkyl, C-*-C 4 halo- alkyl, C C 4 alkoxy, -CN, -NO 2 , C r C 4 alkylthio, C C 4 alkylsulfinyl or by C ⁇ -C 4 alkylsulfonyl; or R 5 and R 6 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 7 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C r C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl mono- or poly-substituted by halogen, C C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, d-C 4 alkyl, d-C 4 halo- alkyl, C C 4 alkoxy, -CN, -NO 2 , C ⁇ -C 4 alkylthio, C C 4 alkylsulfinyl or by C C 4 alkylsulfonyl; R 8 is hydrogen or C C 8 alkyl;
  • R 9 is hydrogen or C C 8 alkyl, or is C C 8 alkyl mono- or poly-substituted by COOH, d-C 8 - alkoxycarbonyl or by -CN, or
  • R 9 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C C 4 alkyl, C C haloalkyl, C C 4 alkoxy, -CN, -NO 2 , C* ⁇ -C 4 alkylthio, C C 4 alkylsulfinyl or by d-C 4 alkylsulfonyl; or R 8 and R 9 together are C 2 -C 5 alkylene;
  • R 10 is hydrogen, d-C alkyl, C 1 -C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • Rn is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C C haloalkyl or C 3 -C 6 haloalkenyl;
  • R 12 is hydrogen, d-C 4 alkyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 13 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl; or
  • R 13 is phenyl or phenyl-d-C 6 alkyl, it being possible for the phenyl ring in turn to be mono- or poly-substituted by halogen, C ⁇ -C alkyl, d-C 4 haloalkyl, d-C 4 alkoxy, -CN, -NO 2 or by -S(O) 2 d-C 8 alkyl, or
  • R 13 is d-C 8 alkyl mono- or poly-substituted by halogen, -CN or by C**-C 4 alkoxy
  • R 14 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C ⁇ -C 8 alkyl mono- or poly- substituted by halogen, -CN or by C ⁇ -C 4 alkoxy;
  • R 15 , R-, 6 and R 17 are each independently of the others d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 - alkynyl, or d-C 8 alkyl mono- or poly-substituted by halogen, -CN or by C**-C 4 alkoxy;
  • R 18 is hydrogen or d-C 8 alkyl;
  • R 19 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C 1 -C 4 alkyl, C C 4 halo- alkyl, d-C 4 alkoxy, -CN, -NO 2> C C 4 alkylthio, C C 4 alkylsulfinyl or by C C 4 alkylsulfonyl; or R ⁇ 8 and R 9 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 20 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C 1 -C 4 alkyl, C ⁇ -C 4 halo- alkyl, C C 4 alkoxy, -CN, -NO 2 , d-C 4 alkylthio, C C 4 alkylsulfinyl or by d-C alkylsulfonyl;
  • R 21 is hydrogen or d-C 8 alkyl;
  • R 22 is hydrogen or d-C 8 alkyl, or is d-C 8 alkyl mono- or poly-substituted by COOH, C ⁇ -C 8 - alkoxycarbonyl or by -CN, or
  • R 22 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C-*-C 4 alkyl, d-C haloalkyl, C ⁇ -C alkoxy,
  • R 2 ⁇ and R 22 together are C 2 -C 5 alkylene
  • R 23 is hydrogen, d-C 4 alkyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 24 is hydrogen, d-C 4 alkyl, C C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 25 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl , C 3 -C 8 alkynyl, C C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 26 is hydrogen or d-C 8 alkyl
  • R 27 is hydrogen or C ⁇ -C 8 alkyl, or is C ⁇ -C 8 alkyl mono- or poly-substituted by COOH, d-C 8 - alkoxycarbonyl or by -CN, or
  • R 27 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C C 4 alkyl, C 1 -C 4 haloalkyl, d-C 4 alkoxy,
  • R 26 and R 27 together are C 2 -C 5 alkylene
  • R 28 is hydrogen or d-C 8 alkyl
  • R 29 and R 30 are each independently of the other hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or
  • R 3 and R 32 are each independently of the other d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or
  • R 36 is hydrogen or d-C 8 alkyl
  • R 37 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C 4 alkyl, C ⁇ -C 4 halo- alkyl, C C 4 alkoxy, -CN, -NO 2 , d-C alkylthio, C C 4 alkylsulfinyl or by C C 4 alkylsulfonyl; or
  • R 36 and R 37 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 38 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C C 8 alkyl, C 3 -C 8 alkenyl or
  • R 40 is hydrogen or d-C 8 alkyl, or is d-C 8 alkyl mono- or poly-substituted by -COOH, d-C 8 - alkoxycarbonyl or by -CN, or
  • R 40 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C-*-C 4 alkyl, d-C 4 haloalkyl, C C 4 alkoxy, -CN, -NO 2 , C r C 4 alkylthio, d-C 4 alkylsulfinyl or by C C 4 alkylsulfonyl; or R 39 and R ⁇ together are C 3 -C 5 alkylene; R 4 ⁇ is hydrogen, C ⁇ -C alkyl, d-C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 42 is hydrogen, C-*-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R ⁇ is hydrogen, d-C alkyl, d-C haloalkyl or C 3 -C 6 cycloalkyl;
  • R ⁇ is hydrogen, C**-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl; or
  • R M is phenyl or phenyl-d-C 6 alkyl, it being possible for the phenyl ring in turn to be mono- or poly-substituted by halogen, C ⁇ -C 4 alkyl, d-C haloalkyl, d-C 4 alkoxy, -CN, -NO 2 or by -S(O) 2 d-C 8 alkyl, or
  • R w is d-C 8 alkyl mono- or poly-substituted by halogen, -CN or by d-C 4 alkoxy;
  • R,i 5 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C**-C 8 alkyl mono- or poly- substituted by halogen, -CN or by d-C alkoxy;
  • R 6 , R 47 and R ⁇ are each independently of the others d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 - alkynyl, or C C 8 alkyl mono- or poly-substituted by halogen, -CN or by C ⁇ -C 4 alkoxy; p is 0 or 1 ;
  • -C(C ⁇ -C 4 alkylthio) NR ⁇ ; or two adjacent R 2 substituents together form a C ⁇ -C 7 alkylene bridge which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C 6 alkyl, the total number of ring atoms being at least 5 and at most 9; or two adjacent R 2 substituents together form a
  • C 2 -C 7 alkenylene bridge which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C 6 alkyl, the total number of ring atoms being at least 5 and at most 9;
  • R 55 is hydrogen or C**-C 8 alkyl
  • R 56 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C- ⁇ -C 4 alkyl, d-C 4 halo- alkyl, C r C 4 alkoxy, -CN, -NO 2 , C C 4 alkylthio, d-C 4 alkylsulfinyl or by C ⁇ -C 4 alkylsulfonyl; or
  • R 55 and R 56 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 57 is hydrogen, C-*-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or is C C 8 alkyl, C 3 -C 8 alkenyl or
  • R 58 is hydrogen or d-C 8 alkyl
  • R 59 is hydrogen or d-C 8 alkyl, or is C C 8 alkyl mono- or poly-substituted by -COOH, d-C 8 - alkoxycarbonyl or by -CN; or
  • R 59 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C 4 alkyl, d-C 4 haloalkyl, d-C 4 alkoxy,
  • R 58 and R 59 together are C 2 -C 5 alkylene
  • R 6 o is hydrogen, d-C 4 alkyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 61 is hydrogen, C C 4 alkyl, C C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 62 is hydrogen, C C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C C haloalkyl or C 3 -C 6 haloalkenyl;
  • R* 53 is hydrogen or d-C 8 alkyl
  • R M is hydrogen or d-C 8 alkyl, or is d-C 8 alkyl mono- or poly-substituted by -COOH, d-C 8 - alkoxycarbonyl or by -CN; or
  • Re 4 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C C 4 alkyl, d-dhaloalkyl, d-C 4 alkoxy,
  • R 63 and R 6 together are C 2 -C 5 alkylene
  • R 65 is hydrogen or d-C 8 alkyl
  • R 66 and R 67 are each independently of the other hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl,
  • Res Reg and R 70 are each independently of the other d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C ⁇ -C 8 alkyl mono- or poly-substituted by halogen, -CN or by C ⁇ -C alkoxy;
  • R 71 and R 73 are each independently of the other hydrogen, d-C 8 alkyl or C ⁇ -C 8 alkoxy;
  • R 72 is C C 8 alkyl
  • R 74 is hydrogen or C-*-C 8 alkyl
  • R 75 is hydrogen, or is d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, each of which may be mono- or poly-substituted by halogen, d-C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, C ⁇ -C 4 alkyl, C ⁇ -C haloalkyl, d-C alkoxy, -CN,
  • R 76 is hydrogen or C ⁇ -C 8 alkyl
  • R 77 is hydrogen or d-C 8 alkyl, or is d-C 8 alkyl mono- or poly-substituted by -COOH, d-C 8 - alkoxycarbonyl or by -CN; or
  • R 77 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C C 4 alkyl, d-C 4 haloalkyl, d-C alkoxy,
  • R 76 and R 77 together are C 2 -C 5 alkylene
  • R 78 and R 7g are each independently of the other hydrogen, C-*-C alkyl, d-C 4 haloalkyl or
  • R 80 is hydrogen, C C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, d-C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 81 is hydrogen or C ⁇ -C 8 alkyl
  • R 82 is hydrogen or d-C 8 alkyl, or is C ⁇ -C 8 alkyl mono- or poly-substituted by -COOH, C C 8 - alkoxycarbonyl or by -CN; or
  • R 82 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C C 4 alkyl, d-C 4 haloalkyl, d-C 4 alkoxy,
  • R 83 is hydrogen or C C 8 alkyl
  • R f -r t is hydrogen, or is C C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, each of which may be mono- or poly-substituted by halogen, d-C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, C C 4 alkyl, d-C 4 haloalkyl, d-C alkoxy, -CN,
  • R 85 is hydrogen or d-C 8 alkyl
  • R 86 is hydrogen or C* ⁇ -C 8 alkyl, or is C ⁇ -C 8 alkyl mono- or poly-substituted by -COOH, C C 8 - alkoxycarbonyl or by -CN; or
  • R 86 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C 4 alkyl, d-C 4 haloalkyl, C C 4 alkoxy,
  • R 85 and R 86 together are C 2 -C 5 alkylene
  • R 87 is hydrogen, d-C alkyl, d-C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 88 is hydrogen, d-C 4 alkyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 89 is hydrogen, C C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, d-C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 90 is hydrogen or C ⁇ -C 8 alkyl
  • R 91 is hydrogen or d-C 8 alkyl, or is d-C 8 alkyl mono- or poly-substituted by -COOH, C C 8 - alkoxycarbonyl or by -CN; or
  • R 91 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C 4 alkyl, d-C 4 haloalkyl, C C 4 alkoxy,
  • R 90 and R 91 together are C 2 -C 5 alkylene
  • R 92 is hydrogen or C-*-C 8 alkyl
  • R 93 is hydrogen, or is d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, each of which may be mono- or poly-substituted by halogen, d-C 4 alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, d-C 4 alkyl, C**-C haloalkyl, C ⁇ -C alkoxy, -CN,
  • R 9 is hydrogen or C ⁇ -C 8 alkyl
  • R 95 is hydrogen or C ⁇ -C 8 alkyl, or is d-C 8 alkyl mono- or poly-substituted by -COOH, C r C 8 - alkoxycarbonyl or by -CN; or
  • R 95 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C ⁇ -C 4 alkyl, d-dhaloalkyl, d-C alkoxy,
  • R 94 and R 95 together are C 2 -C 5 alkylene;
  • R 96 is hydrogen, C C 4 alkyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 97 is hydrogen, C C alkyl, d-C haloalkyl or C 3 -C 6 cycloalkyl;
  • R 98 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, d-dhaloalkyl or C 3 -C 6 haloalkenyl;
  • R 99 is hydrogen or d-C 8 alkyl
  • R 10 o is hydrogen or d-C 8 alkyl, or is C ⁇ -C 8 alkyl mono- or poly-substituted by -COOH, C C 8 - alkoxycarbonyl or by -CN; or
  • R 100 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C 4 alkyl, d-C 4 haloalkyl, d-dalkoxy,
  • R 99 and R 100 together are C 2 -C 5 alkylene
  • R 10 ⁇ is hydrogen or d-C 8 alkyl, or an agrochemically acceptable salt or any stereoisomer or tautomer of a compound of formula I, and
  • Metamifop (Dongbu Hannong; Code No. DBH 129) is known as a herbicide and is registered under CAS Reg. No. [256412-89-2].
  • Fluazolate (Monsanto; Code No. JV-485, MON 48500) is also known as a herbicide under the common name isopropazole and is registered under CAS Reg. No. [174514-07-9].
  • the compound of formula 2.1 is known as a herbicide under the common name benfluamid (UBE; Code No. UBH 820) and is registered under CAS Reg. No. [113604-08-7].
  • Flufenpyr is known as a herbicide and is registered under CAS Reg. No. [188489-06-7].
  • the invention also includes the salts that the compounds of formula I having acid hydrogen, especially the derivatives having carboxylic acid groups (e.g. carboxyl-substituted alkyl, alkenyl and alkynyl groups), are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • carboxylic acid groups e.g. carboxyl-substituted alkyl, alkenyl and alkynyl groups
  • quaternary ammonium bases e.g., quaternary ammonium bases.
  • alkali metal and alkaline earth metal hydroxides used as salt formers emphasis is to be given to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to those of sodium and potassium.
  • Suitable amines for ammonium salt formation are ammonia as well as primary, secondary and tertiary C ⁇ -C-* 8 alkylamines, d-dhydroxyalkyl- amines and C 2 -C alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl- hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octa
  • -SO 2 R 47 -OSO- ⁇ R ⁇ or d-C 8 alkyl, or is C C 8 alkyl mono- or poly-substituted by halogen, -CN or by -CO 2 R 57 ;
  • R 38 is hydrogen or d-C 8 alkyl
  • R 41 is hydrogen or C C 4 alkyl
  • R 42 is d-C 8 alkyl.
  • -OSO 2 R ⁇ 7 d-C 8 alkyl or C 2 -C 8 alkenyl, or is d-C 8 alkyl mono- or poly-substituted by -CN;
  • R 10 is hydrogen or d-C 4 alkyl
  • R 36 and R 37 are hydrogen
  • R 38 is hydrogen or d-C 8 alkyl
  • R 41 is hydrogen or C ⁇ -C 4 alkyl
  • R 42 is d-C 8 alkyl
  • R 3 and R 4 are each independently of the other hydrogen or d-C 4 alkyl.
  • R ⁇ is halogen or -CN, or is d-C 8 alkyl substituted by -CN, or is C ⁇ -C 8 alkoxy.
  • n 1 or 2
  • Ri occupying the 3- and/or 5-position on the pyridine ring.
  • R-i is hydrogen, fluorine, chlorine, bromine, methoxy, difluoromethoxy, trifluoromethyl or isopropylthio;
  • R 2 is cyanomethyl, chlorine or bromine
  • R 3 and R are hydrogen; n is 1 or 2 and m is 1.
  • Preferred synergistic mixtures according to the invention for controlling weeds and grasses in crops of cereals comprise, as co-herbicides under b), compounds selected from the group: triasulfuron, prosulfuron, clodinafop-propargyl, terbutryn, fenoxaprop-P-ethyl, diclof op-methyl, tralkoxydim, butroxydim, amidosulfuron, chlorsulfuron, ethoxysulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, thifensulfuron-methyl, tribenuron-methyl, imazamethabenz-methyl, flucarbazone-sodium, iodosulfuron-methyl- sodium, florasulam, flumetsulam, metosulam, chlortoluron, methabenzthiazuron, bromoxynil,
  • Preferred synergistic mixtures according to the invention for controlling weeds and grasses in crops of rice comprise, as co-herbicides under b), compounds selected from the group: pretilachlor, cinosulfuron, triasulfuron, fenclorim, pyriftalid, clodinafop-propargyl, metolachlor, S-metolachlor, mixtures of metolachlor and S-metolachlor, preferably mixtures thereof containing 50-90 %, especially 70-90 % S-metolachlor, bensulfuron-methyl, imazosulfuron, pyrazosulfuron-ethyl, metsulfuron-methyl, azimsulfuron, mefenacet, cyhalof op-butyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, cafenstrole, glyphosate, S-glufosinate
  • synergistic mixtures according to the invention for controlling weeds and grasses in crops of cereals and rice comprise, as co-herbicides under b), compounds selected from the group: amidosulfuron, azimsulfuron, bensulfuron-methyl, bromoxynil, carfentrazone-ethyl, chlorsulfuron, cinosulfuron, clodinafop-propargyl, cyclosulfamuron, cyhalof op-butyl, dicamba, diclofop-methyl, ethoxysulfuron, fenoxaprop-P-ethyl, flazasulfuron, florasulam, fluazolate, flufenacet, flupyrsulfuron, flupyrsulfuron-methyl-sodium, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron-methyl, benfuresate, bent
  • the combination of the compound of formula I with one or more active ingredients selected from the co-herbicides under b) exceeds the additive effect on the weeds to be controlled that is to be expected in principle and thus broadens the range of action of the individual active ingredients especially in two respects: firstly, the rates of application of the individual compounds of formula I and co-herbicides under b) are reduced while a good level of action is maintained and, secondly, the composition according to the invention achieves a high level of weed control also in those cases where the individual substances, in the low rates of application range, have become useless from the agronomic standpoint.
  • composition according to the invention while retaining excellent control of weeds in crops of useful plants, also allows greater flexibility in succeeding crops.
  • the composition according to the invention can be used against a large number of agronomically important weeds, such as Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • the composition according to the invention is suitable for all methods of application conventionally used in agriculture, e.g.
  • composition according to the invention is suitable especially for controlling weeds in crops of useful plants, such as rape, sugar beet, sugar cane, plantation crops, soybeans and, especially, cereals, rice and maize, and also for non-selective weed control.
  • Crops are to be understood to mean also those crops which have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering.
  • composition according to the invention comprises the compound of formula I and the co- herbicides under b) in any mixing ratio, but usually has an excess of one component over the others.
  • the mixing ratios (ratios by weight) of the compound of formula I and the co-herbicides under b) are from 1 :2000 to 2000:1 , especially from 200:1 to 1 :200.
  • the rate of application may vary within wide limits and depends on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the active ingredient mixture according to the invention can generally be applied at a rate of from 1 to 5000 g of active ingredient mixture per ha.
  • the mixtures of the compound of formula I with the co-herbicides under b) may be used in unmodified form, that is to say as obtained in the synthesis.
  • they are formulated in customary manner, together with the adjuvants conventionally used in formulation technology, such as solvents, solid carriers or surfactants, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions i.e. the compositions, preparations or mixtures comprising the compounds of formula I and the co-herbicides under b), and also, where appropriate, one or more solid or liquid formulation adjuvants, are prepared in a manner known per se, e.g. by intimately mixing and/or grinding the active ingredients with the formulation adjuvants, e.g. solvents or solid carriers.
  • formulation adjuvants e.g. solvents or solid carriers.
  • surface-active compounds surfactants
  • surfactants may also be used in the preparation of the formulations.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • anionic, non-ionic and cationic surfactants examples include WO 97/34485, pages 7 and 8.
  • Also suitable in the preparation of the herbicidal compositions according to the invention are the surfactants conventionally used in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., “Tensid-Taschenbuch", Carl Hanser Verlag, Kunststoff/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol l-lll, Chemical Publishing Co., New York, 1980-81.
  • the herbicidal formulations usually contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture comprising a compound of formula I together with the co-herbicides under b), from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • Emulsifiable concentrates active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
  • Dusts active ingredient mixture: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient mixture: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient mixture: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient mixture: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • Emulsifiable concentrates a) b) c) d) active ingredient mixture 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 % castor oil polyglycol ether 4 % - 4 % 4 %
  • Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
  • the solutions are suitable for use in the form of microdrops.
  • Wettable powders a) b) c) d) active ingredient mixture 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2% -
  • the active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • F4. Coated granules a) b) c) active ingredient mixture 0.1 % 5% 15% highly dispersed silicic acid 0.9 % 2% 2% inorganic carrier 99.0 % 93% 83%
  • the active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.
  • the finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol.
  • Non-dusty coated granules are obtained in this manner.
  • the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
  • Suspension concentrates a) b) c) d) active ingredient mixture 3 % 10 % 25 % 50 % ethylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether - 1 % 2 % -
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
  • Y percentage herbicidal action on treatment with a co-herbicide under b) at a rate of application of q kg per hectare, compared with the untreated control.
  • test plants are grown to the 2- to 3-leaf stage in plastics pots under greenhouse conditions. A standard soil is used as cultivation substrate.
  • the herbicides are applied to the test plants both alone and in admixture.
  • Application is carried out using an aqueous suspension of the test compounds in 500 litres of water per ha. The rates of application depend on the optimum concentrations determined under field conditions and greenhouse conditions.
  • the present invention accordingly relates also to a selectively herbicidal composition for controlling grasses and weeds in crops of useful plants, especially in crops of cereals, rice and maize, that comprises a compound of formula I, one or more compounds selected from the co-herbicides under b), and a safener (counter agent, antidote) that protects the useful plants, but not the weeds, against the phytotoxic action of the herbicide, as well as to the use of such a composition in the control of weeds in crops of useful plants.
  • a selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of ab) an amount, effective for herbicide synergism, of a compound of formula I and one or more compounds selected from the co-herbicides under b) and c) an amount, effective for herbicide antagonism, of a compound selected from the compound of formula 3.1
  • the compounds of formulae 3.1 to 3.16 are known and are described, for example, in the "Pesticide Manual", 12th Edition, British Crop Protection Council, 2000 under the entry numbers 65 (formula 3.1 , benoxacor), 325 (formula 3.2, fenclorim), 163 (formula 3.3, cloquintocet-mexyl), 492 (formula 3.4, mefenpyr-diethyl), 401 (formula 3.5, furilazole), 389 (formula 3.8, fluxofenim), 225 (formula 3.9, dichlormid) and 376 (formula 3.10, flurazole).
  • the compound of formula 3.11 is known under the designation MON 4660 (Monsanto) and is described, for example, in EP-A-0 436 483.
  • the free acid and salts of cloquintocet-mexyl are known, for example, from WO 02/34048, and the free acid and salts of mefenpyr-diethyl (formula 3.4) are known, for example, from WO 01/17353.
  • the compound of formula 3.6 (AC 304415) is described, for example, in EP-A-0 613 618, and the compound of formula 3.7 in DE-A-29 48 535.
  • the compounds of formula 3.12 are known under the common names isoxadifen and isoxadifen-ethyl, are described in DE-A-43 31 448 and are registered under the CAS Reg. Nos. [209866-92-2] and [163520- 33-0], and the compound of formula 3.13 is described in DE-A-35 25 205.
  • the compound of formula 3.14 is known, for example, from US-A-5 215 570, and the compound of formula 3.15 from EP-A-0 929 543.
  • the compound of formula 3.16 is described in WO 99/00020.
  • the other 3-(5-tetrazolyl- carbonyl)-2-quinolones described in WO 99/00020 especially the compounds specifically disclosed in Tables 1 and 2 on pages 21 to 29, are also suitable for protecting crop plants against the phytotoxic action of the compounds of formula I.
  • the invention relates also to a selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) a herbicidally effective amount of a compound of formula I and c) an amount, effective for herbicide antagonism, of a compound selected from the compounds of formulae 3.1 , 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.10, 3.11 , 3.12, 3.13, 3.14,
  • Preferred mixtures according to the invention comprise as safener a compound selected from the compounds of formulae 3.1 , 3.3 and 3.8.
  • Such safe/iers are suitable especially for those compositions according to the invention that comprise the above-mentioned preferred co-herbicides under b).
  • Combinations of the compound of formula I with the compound of formula 3.3 have been found to be very especially effective compositions.
  • Such a composition is preferably used together with clodinafop-propargyl (156).
  • the invention relates also to a method for the selective control of weeds in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with a herbicidally effective amount of a herbicide of formula I, optionally one or more herbicides selected from the co-herbicides under b), and an amount, effective for herbicide antagonism, of a safener from formulae 3.1 to 3.16.
  • Crops are to be understood to mean also those crops which have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering.
  • the weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, such as, for example Stellaria, Agrostis, Digitaria, Avena, Apera, Brachiaria, Phalaris, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Panicum, Bromus, Alopecurus, Sorghum halepense, Sorghum bicolor, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Agrostis, Digitaria, Avena, Apera, Brachiaria, Phalaris, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Panicum, Bromus,
  • Areas of cultivation include the areas of ground on which the crop plants are already growing or which have been sown with the seed material of those crop plants, as well as ground intended for the cultivation of such crop plants.
  • a safener of formula 3.1 to 3.16 can be used in the pretreatment of the seed material of the crop plant (dressing of the seeds or cuttings) or can be introduced into the soil before or after sowing. It can, however, also be applied, either alone (so-called “split application”) or together with the herbicide, after emergence of the plants.
  • the treatment of the plants or seeds with the safener can therefore in principle be carried out independently of the time at which the herbicide is applied but implies a period of time in which herbicide and safener are still able to meet in order that the safening action can subsequently come about at all. So-called “split application” must be distinguished from separate application.
  • the plants can, however, also be treated by simultaneous application of herbicide and safener (e.g. in the form of a tank mixture).
  • the ratio of the rate of application of safener to the rate of application of herbicide depends largely on the method of application.
  • the ratio of herbicides to safener is generally from 100:1 to 1 :10, preferably from 20:1 to 1 :1.
  • the rate of application of herbicides is generally from 0.001 to 2 kg per ha, but preferably from 0.005 to 0.5 kg per ha.
  • compositions according to the invention are suitable for all methods of application conventionally used in agriculture, e.g. pre-emergence application, post-emergence application and seed dressing.
  • seed dressing generally from 0.001 to 10 g of safener per kg of seed, preferably from 0.05 to 2 g of safener per kg of seed, are applied.
  • the safener solutions used contain the active ingredient in a concentration of from 1 to 10 000 ppm, preferably from 100 to 1000 ppm.
  • the safeners of formulae 3.1 to 3.16 or combinations of those safeners with a herbicide of formula I and optionally one or more herbicides selected from the co-herbicides under b) are advantageously formulated together with adjuvants customary in formulation technology, e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • formulations are described, for example, in WO 97/34485, pages 9 to 13.
  • the formulations are prepared in known manner, e.g. by intimately mixing and/or grinding the active ingredients with liquid or solid formulation adjuvants, e.g. solvents or solid carriers.
  • liquid or solid formulation adjuvants e.g. solvents or solid carriers.
  • surface-active compounds surfactants
  • Solvents and solid carriers suitable for that purpose are mentioned, for example, in WO 97/34485, on page 6.
  • the co-herbicides under b) and the safeners of formulae 3.1 to 3.16 to be formulated there come into consideration as surface- active compounds non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • surface- active compounds non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8.
  • Also suitable for the preparation of the herbicidal compositions according to the invention are the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., “Tensid-Taschenbuch", Carl Hanser Verlag, Kunststoff/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol. Nil, Chemical Publishing Co., New York, 1980-81.
  • the herbicidal formulations usually contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture comprising a compound of formula I, a compound selected from the co-herbicides under b) and the safeners of formulae 3.1 to 3.16, from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • a solid or liquid formulation adjuvant preferably from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil)
  • antifoams e.g. silicone oil
  • preservatives e.g. silicone oil
  • viscosity regulators binders
  • tackifiers e.g. silicone oil
  • fertilisers or other active ingredients e.g.
  • various methods and techniques come into consideration, such as, for example, the following:
  • Seed dressing a) Dressing of the seeds with a wettable powder formulation of a compound from formulae 3.1 to 3.16 by shaking in a vessel until uniformly distributed over the seed surface (dry dressing). In that procedure approximately from 1 to 500 g of a compound from formulae 3.1 to 3.16 (4 g to 2 kg of wettable powder) are used per 100 kg of seed material. b) Dressing of the seeds with an emulsifiable concentrate of a compound from formulae 3.1 to 3.16 according to method a) (wet dressing). c) Dressing by immersing the seed material for from 1 to 72 hours in a liquor comprising from 100 to 1000 ppm of a compound from formulae 3.1 to 3.16 and optionally subsequently drying the seeds (immersion dressing).
  • Dressing the seed material or treating the germinated seedling are naturally the preferred methods of application, because treatment with the active ingredients is directed entirely at the target crop.
  • a liquid formulation of a mixture of antidote and herbicide is used (ratio by weight of the one to the other from 10:1 to 1 :100), the rate of application of herbicide being from 0.005 to
  • the compound from formulae 3.1 to 3.16 is introduced into the open, sown seed furrow in the form of an emulsifiable concentrate, wettable powder or granules. Once the seed furrow has been covered over, the herbicide is applied in the usual manner pre-emergence. iv) Controlled release of active ingredient
  • the compound from formulae 3.1 to 3.16 is applied in solution to mineral carrier granules or polymerised granules (urea/formaldehyde) and dried. If desired, it is also possible to apply a coating that allows the active ingredient to be released in metered amounts over a specific period of time (coated granules).
  • Preferred formulations have especially the following compositions:
  • Emulsifiable concentrates active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
  • Dusts active ingredient mixture: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient mixture: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient mixture: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient mixture: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • Emulsifiable concentrates a) b) c) d) active ingredient mixture 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 6 %% 8 % 6 % 8 % castor oil polyglycol ether 4 % . 4 % 4 %
  • Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
  • the solutions are suitable for use in the form of microdrops.
  • F3. Wettable powders a) b) c) d) active ingredient mixture 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2% -
  • the active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • the active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.
  • the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
  • Suspension concentrates a) b) c) d) active ingredient mixture 3% 10% 25% 50% ethylene glycol 5% 5% 5% nonylphenol polyglycol ether - 1 % 2% -
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
  • test plants are grown in plastics pots under greenhouse conditions to the 4-leaf stage. At that stage, either the herbicides alone or the mixtures of the herbicides with the test compounds being tested as safeners are applied to the test plants.
  • the test compounds are applied in the form of an aqueous suspension prepared from a 25 % wettable powder (Example F3, b)), using 500 litres of water per ha. 4 weeks after application, the phytotoxic action of the herbicides on the crop plants, e.g. maize and cereals, is evaluated using a percentage scale. 100 % indicates that the test plant has died, 0 % indicates no phytotoxic action.
  • the mixtures according to the invention exhibit a good action in this test.

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Abstract

Herbicidal composition that, in addition to comprising customary inert formulation adjuvants, comprises a) a compound of formula (I), wherein the substituents R1, R2, R3 and R4, and the suffixes n and m are as defined in claim 1, or an agronomically acceptable salt of that compound, and b) a synergistically effective amount of one or more co-herbicides. The compositions according to the invention may also comprise a safener.

Description

HERBICIDAL COMPOSITION COMPRISING PHENYLPROPYNYLOXYPYRIDINE COMPOUNDS
The present invention relates to a novel herbicidal composition comprising a herbicidal active ingredient combination that is suitable for the selective control of weeds in crops of useful plants, for example in crops of cotton, soybeans, sugar beet, sugar cane, plantation crops, rape and, especially, cereals, rice and maize. The invention relates also to a method of controlling weeds in crops of useful plants and to the use of the novel composition for that purpose.
The compounds of formula
wherein the substituents Ri to R4, and the suffixes n and m, are as defined hereinbelow, exhibit herbicidal action.
The compounds of formula I and their preparation are known, for example, from WO
02/28182.
Surprisingly, it has now been found that a combination of variable amounts of active ingredients, that is to say a compound of formula I together with one or more of the herbicidal active ingredients indicated below, which are known and some of which are also commercially available, exhibits a synergistic action that is capable of controlling, both pre- emergence and post-emergence, the majority of weeds occurring especially in crops of useful plants.
There is therefore proposed in accordance with the present invention a novel synergistic composition for the selective control of weeds which, in addition to comprising customary inert formulation adjuvants, comprises as active ingredient a mixture of a) a herbicidally effective amount of a compound of formula I
wherein n is O, 1 , 2, 3 or 4; each R-, independently is halogen, -CN, -SCN, -SF5, -NO2, -NR5R6, -CO2R7, -CONR8R9, -COR12, -OR13, -SR14, -SOR15, -SO2R16, -OSO2R17, d-C8alkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl; or is C**-C8alkyl, C2-C8alkenyl or C2-C8alkynyl mono- or poly- substituted by halogen, -CN, -NO2, -NR18R19, -COsR∞, -CONR21R22, -COR23, -C(R24)=NOR25, -C(S)NR26R27, -C(d-C4alkylthio)=NR28, -OR29, -SR30, -SOR31, -SO2R32 or by C3-C6cycloalkyl; or each Ri is C3-C6cycloalkyl mono- or poly-substituted by halogen, -CN, -NO2, -NR18R19, -CO2R20, -CONR21R22) -COR23, -C(R24)=NOR25, -C(S)NR26R27, -C(d-C4alkylthio)=NR28) - SR30, -SOR31, -SO2R32 or by C3-C6cycloalkyl; or each RT independently is phenyl, which may in turn be mono- or poly-substituted by halogen, d-C4alkyl, C C4haloalkyl, C C4alkoxy, -CN, -NO2> CrC4alkylthio, d-C4alkylsulfinyl or by d-C alkylsulfonyl; or two adjacent Ri substituents together form a C C7alkylene bridge which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by C-*-C6alkyl, the total number of ring atoms being at least 5 and at most 9; or two adjacent R, substituents together form a C2-C7alkenylene bridge which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C6alkyl, the total number of ring atoms being at least 5 and at most 9; R3 and R4 are each independently of the other hydrogen, halogen, -CN, d-C4alkyl or d-C alkoxy; or
R3 and R4 together are C2-C5alkylene; R5 is hydrogen or d-C8alkyl;
R6 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl; it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, C-*-C4halo- alkyl, C C4alkoxy, -CN, -NO2, CrC4alkylthio, C C4alkylsulfinyl or by Cι-C4alkylsulfonyl; or R5 and R6 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R7 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- or poly-substituted by halogen, C C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-C4halo- alkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; R8 is hydrogen or C C8alkyl;
R9 is hydrogen or C C8alkyl, or is C C8alkyl mono- or poly-substituted by COOH, d-C8- alkoxycarbonyl or by -CN, or
R9 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C C4alkyl, C C haloalkyl, C C4alkoxy, -CN, -NO2, C*ι-C4alkylthio, C C4alkylsulfinyl or by d-C4alkylsulfonyl; or R8 and R9 together are C2-C5alkylene; R10 is hydrogen, d-C alkyl, C1-C4haloalkyl or C3-C6cycloalkyl;
Rn is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C haloalkyl or C3-C6haloalkenyl; R12 is hydrogen, d-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; R13 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl; or
R13 is phenyl or phenyl-d-C6alkyl, it being possible for the phenyl ring in turn to be mono- or poly-substituted by halogen, Cι-C alkyl, d-C4haloalkyl, d-C4alkoxy, -CN, -NO2 or by -S(O)2d-C8alkyl, or
R13 is d-C8alkyl mono- or poly-substituted by halogen, -CN or by C**-C4alkoxy; R14 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is Cι-C8alkyl mono- or poly- substituted by halogen, -CN or by Cι-C4alkoxy;
R15, R-,6 and R17 are each independently of the others d-C8alkyl, C3-C8alkenyl or C3-C8- alkynyl, or d-C8alkyl mono- or poly-substituted by halogen, -CN or by C**-C4alkoxy; R18 is hydrogen or d-C8alkyl;
R19 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C1-C4alkyl, C C4halo- alkyl, d-C4alkoxy, -CN, -NO2> C C4alkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; or Rι8 and R 9 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R20 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C1-C4alkyl, Cι-C4halo- alkyl, C C4alkoxy, -CN, -NO2, d-C4alkylthio, C C4alkylsulfinyl or by d-C alkylsulfonyl; R21 is hydrogen or d-C8alkyl;
R22 is hydrogen or d-C8alkyl, or is d-C8alkyl mono- or poly-substituted by COOH, Cι-C8- alkoxycarbonyl or by -CN, or
R22 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C-*-C4alkyl, d-C haloalkyl, Cι-C alkoxy,
-CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by Cι-C4alkylsulfonyl; or
R2ι and R22 together are C2-C5alkylene;
R23 is hydrogen, d-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R24 is hydrogen, d-C4alkyl, C C4haloalkyl or C3-C6cycloalkyl;
R25 is hydrogen, Cι-C8alkyl, C3-C8alkenyl , C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl;
R26 is hydrogen or d-C8alkyl;
R27 is hydrogen or Cι-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by COOH, d-C8- alkoxycarbonyl or by -CN, or
R27 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C C4alkyl, C1-C4haloalkyl, d-C4alkoxy,
-CN, -NO2, d-C4alkylthio, C C4alkylsulfinyl or by d-C4alkylsulfonyl; or
R26 and R27 together are C2-C5alkylene;
R28 is hydrogen or d-C8alkyl;
R29 and R30 are each independently of the other hydrogen, d-C8alkyl, C3-C8alkenyl or
C3-C8alkynyl, or d-C8alkyl mono- or poly-substituted by halogen, -CN or by Cι-C alkoxy;
R3 and R32 are each independently of the other d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or
Cι-C8alkyl mono- or poly-substituted by halogen, -CN or by d-C4alkoxy; m is 0, 1 , 2, 3, 4 or 5; each R2 independently is halogen, -CN, -SCN, -SF5, -NO2, -NR36R37, -CO2R38,
-C(R41)=NOR42, -COR43, -OR44, -SR45, -SOR^, -SO2R47) OSO-^R^ -N([CO]pR49)COR5o,
-N(OR5ι)COR52, -N(R53)CO2R54 or -N-phthalimide;
R36 is hydrogen or d-C8alkyl; and
R37 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, Cι-C4halo- alkyl, C C4alkoxy, -CN, -NO2, d-C alkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; or
R36 and R37 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R38 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is C C8alkyl, C3-C8alkenyl or
C3-C8alkynyl mono- or poly-substituted by halogen, C C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, d-C alkyl, C C4halo- alkyl, CrC4alkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or by d-C4alkylsulfonyl; R39 is hydrogen or d-C8alkyl;
R40 is hydrogen or d-C8alkyl, or is d-C8alkyl mono- or poly-substituted by -COOH, d-C8- alkoxycarbonyl or by -CN, or
R40 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C-*-C4alkyl, d-C4haloalkyl, C C4alkoxy, -CN, -NO2, CrC4alkylthio, d-C4alkylsulfinyl or by C C4alkylsulfonyl; or R39 and R^ together are C3-C5alkylene; R4ι is hydrogen, Cι-C alkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R42 is hydrogen, C-*-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl; R^ is hydrogen, d-C alkyl, d-C haloalkyl or C3-C6cycloalkyl; R^ is hydrogen, C**-C8alkyl, C3-C8alkenyl or C3-C8alkynyl; or
RM is phenyl or phenyl-d-C6alkyl, it being possible for the phenyl ring in turn to be mono- or poly-substituted by halogen, Cι-C4alkyl, d-C haloalkyl, d-C4alkoxy, -CN, -NO2 or by -S(O)2d-C8alkyl, or
Rw is d-C8alkyl mono- or poly-substituted by halogen, -CN or by d-C4alkoxy; R,i5 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is C**-C8alkyl mono- or poly- substituted by halogen, -CN or by d-C alkoxy;
R 6, R47 and R^ are each independently of the others d-C8alkyl, C3-C8alkenyl or C3-C8- alkynyl, or C C8alkyl mono- or poly-substituted by halogen, -CN or by Cι-C4alkoxy; p is 0 or 1 ;
R49, R50. R51, R52. Rδ3 and R*^ are each independently of the others hydrogen, d-C8alkyl, or phenyl which may in turn be mono- or poly-substituted by halogen, d-C8alkyl, d-C4halo- alkyl, C C4alkoxy, -CN, -NO2, d-C8alkylthio, C C8alkylsulfinyl or by Cι-C8alkylsulfonyl; or each R2 independently is Cι-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by halogen, -CN, -NO2, -NR55R56, -CO2R57, -CONR58R59, -COR60> -C(R61)=NOR62, -C(S)NR63R6 , -C(d-C4alkylthio)=NR65> -OR66, -SR67, -SOR68, -SO2R69, -O(SO2)R70) -N(R71)CO2R72, -N(R73)COR74 or by C3-C6cycloalkyl; or each R2 independently is C2-C8alkenyl, or is C2-C8alkenyl mono- or poly-substituted by -CN, -NO2, -CO2R75, -CONR76Rτ7, -COR78, -C(R79)=NOR80> -C(S)NR81R82, or by C3-C6cycloalkyl; or each R2 independently is C2-C8alkynyl, or is C2-C8alkynyl mono- or poly-substituted by halogen, -CN, -CO2Rβ4, -CONR85R86, -COR87l -C(R88)=NOR89, -C(S)NR90R91,
-C(C C4alkylthio)=NR92 or by C3-C6cycloalkyl; or each R2 independently is C3-C6cycloalkyl, or is C3-C6cycloalkyl mono- or poly-substituted by halogen, -CN, -CO2R93, -CONR94R95> -COR96, -C(R97)=NOR98, -C(S)NR99R100 or by
-C(Cι-C4alkylthio)=NRι ; or two adjacent R2 substituents together form a Cι-C7alkylene bridge which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C6alkyl, the total number of ring atoms being at least 5 and at most 9; or two adjacent R2 substituents together form a
C2-C7alkenylene bridge which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C6alkyl, the total number of ring atoms being at least 5 and at most 9;
R55 is hydrogen or C**-C8alkyl;
R56 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C-ι-C4alkyl, d-C4halo- alkyl, CrC4alkoxy, -CN, -NO2, C C4alkylthio, d-C4alkylsulfinyl or by Cι-C4alkylsulfonyl; or
R55 and R56 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R57 is hydrogen, C-*-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is C C8alkyl, C3-C8alkenyl or
C3-C8alkynyl mono- or poly-substituted by halogen, C-*-C alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, Cι-C4alkyl, Cι-C4halo- alkyl, d-C4alkoxy, -CN, -NO2, C C4alkylthio, d-C4alkylsulfinyl or by C C4alkylsulfonyl;
R58 is hydrogen or d-C8alkyl;
R59 is hydrogen or d-C8alkyl, or is C C8alkyl mono- or poly-substituted by -COOH, d-C8- alkoxycarbonyl or by -CN; or
R59 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-C4haloalkyl, d-C4alkoxy,
-CN, -NO2) d-dalkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; or
R58 and R59 together are C2-C5alkylene;
R6o is hydrogen, d-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R61 is hydrogen, C C4alkyl, C C4haloalkyl or C3-C6cycloalkyl;
R62 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C haloalkyl or C3-C6haloalkenyl; and
R*53 is hydrogen or d-C8alkyl; RM is hydrogen or d-C8alkyl, or is d-C8alkyl mono- or poly-substituted by -COOH, d-C8- alkoxycarbonyl or by -CN; or
Re4 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C C4alkyl, d-dhaloalkyl, d-C4alkoxy,
-CN, -NO2, C-ι-C4alkylthio, C1-C4alkylsulfinyl or by C C4alkylsulfonyl; or
R63 and R6 together are C2-C5alkylene;
R65 is hydrogen or d-C8alkyl;
R66 and R67 are each independently of the other hydrogen, d-C8alkyl, C3-C8alkenyl,
C3-C8alkynyl, or d-C8alkyl mono- or poly-substituted by halogen, -CN or by Cι-C4alkoxy;
Res Reg and R70 are each independently of the other d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl mono- or poly-substituted by halogen, -CN or by Cι-C alkoxy;
R71 and R73 are each independently of the other hydrogen, d-C8alkyl or Cι-C8alkoxy;
R72 is C C8alkyl;
R74 is hydrogen or C-*-C8alkyl;
R75 is hydrogen, or is d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- or poly-substituted by halogen, d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, Cι-C4alkyl, Cι-C haloalkyl, d-C alkoxy, -CN,
-NO2) d-dalkylthio, d-C alkylsulfinyl or by d-C4alkylsulfonyl;
R76 is hydrogen or Cι-C8alkyl;
R77 is hydrogen or d-C8alkyl, or is d-C8alkyl mono- or poly-substituted by -COOH, d-C8- alkoxycarbonyl or by -CN; or
R77 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C C4alkyl, d-C4haloalkyl, d-C alkoxy,
-CN, -NO2, Cι-C4alkylthio, d-C4alkylsulfinyl or by C C4alkylsulfonyl; or
R76 and R77 together are C2-C5alkylene;
R78 and R7g are each independently of the other hydrogen, C-*-C alkyl, d-C4haloalkyl or
C3-C6cycloalkyl;
R80 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl;
R81 is hydrogen or Cι-C8alkyl;
R82 is hydrogen or d-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by -COOH, C C8- alkoxycarbonyl or by -CN; or
R82 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C C4alkyl, d-C4haloalkyl, d-C4alkoxy,
-CN, -NO2) d-dalkylthio, d-C4alkylsulfinyl or by C C4alkylsulfonyl; or R8*i and R82 together are C2-C5alkylene;
R83 is hydrogen or C C8alkyl;
Rf-rt is hydrogen, or is C C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- or poly-substituted by halogen, d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, C C4alkyl, d-C4haloalkyl, d-C alkoxy, -CN,
-NO2) d-C4alkylthio, Cι-C4alkylsulfinyl or by d-C4alkylsulfonyl;
R85 is hydrogen or d-C8alkyl;
R86 is hydrogen or C*ι-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by -COOH, C C8- alkoxycarbonyl or by -CN; or
R86 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-C4haloalkyl, C C4alkoxy,
-CN, -NO2, d-C4alkylthio, C C4alkylsulfinyl or by d-C4alkylsulfonyl; or
R85 and R86 together are C2-C5alkylene;
R87 is hydrogen, d-C alkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R88 is hydrogen, d-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R89 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl;
R90 is hydrogen or Cι-C8alkyl;
R91 is hydrogen or d-C8alkyl, or is d-C8alkyl mono- or poly-substituted by -COOH, C C8- alkoxycarbonyl or by -CN; or
R91 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-C4haloalkyl, C C4alkoxy,
-CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by d-C4alkylsulfonyl; or
R90 and R91 together are C2-C5alkylene;
R92 is hydrogen or C-*-C8alkyl;
R93 is hydrogen, or is d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- or poly-substituted by halogen, d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, C**-C haloalkyl, Cι-C alkoxy, -CN,
-NO2, d-dalkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl;
R9 is hydrogen or Cι-C8alkyl;
R95 is hydrogen or Cι-C8alkyl, or is d-C8alkyl mono- or poly-substituted by -COOH, CrC8- alkoxycarbonyl or by -CN; or
R95 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, Cι-C4alkyl, d-dhaloalkyl, d-C alkoxy,
-CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by Cι-C4alkylsulfonyl; or R94 and R95 together are C2-C5alkylene;
R96 is hydrogen, C C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R97 is hydrogen, C C alkyl, d-C haloalkyl or C3-C6cycloalkyl;
R98 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, d-dhaloalkyl or C3-C6haloalkenyl;
R99 is hydrogen or d-C8alkyl;
R10o is hydrogen or d-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by -COOH, C C8- alkoxycarbonyl or by -CN; or
R100 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-C4haloalkyl, d-dalkoxy,
-CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by C C4alkylsulfonyl; or
R99 and R100 together are C2-C5alkylene; and
R10ι is hydrogen or d-C8alkyl, or an agrochemically acceptable salt or any stereoisomer or tautomer of a compound of formula I, and
b) a synergistically effective amount of one or more compounds selected from the group consisting of the co-herbicides: triasulfuron (773), prosulfuron (657), clodinafop-propargyl (156), terbutryn (740), dicamba (222), fenoxaprop-P-ethyl (331 ), metamifop, diclofop-methyl (232), tralkoxydim (767), butroxydim (104), amidosulfuron (24), chlorsulfuron (146), ethoxysulfuron (307), flupyrsulfuron (374), flupyrsulfuron-methyl-sodium (374), metsulfuron-methyl (536), sulfosulfuron (714), thifensulfuron-methyl (754), tribenuron-methyl (778), imazamethabenz- methyl (438), flucarbazone-sodium (357), iodosulfuron-methyl-sodium (454), florasulam (351 ), flumetsulam (366), metosulam (533), chlorotoluron (142), isoproturon (464), methabenzthiazuron (510), bromoxynil (93), ioxynil (455), pyridate (672), bifenox (75), fluoroglycofen-ethyl (371 ), carfentrazone-ethyl (119), fluazolate (355), diflufenican (245), flurtamone (382), glyphosate (407), sulfosate (407), glufosinate (406), S-glufosinate, bialaphos (bilanafos; (77)), ethalfluralin (298), pendimethalin (599), 2,4-DB (211 ), dichlorprop (2,4-DP; (228)), MCPA (485), MCPB (487), mecoprop (MCPP; (489)), mecoprop-P (490), clopyralid (162), fluroxypyr (380), quinmerac (682), benazolin-ethyl (59), difenzoquat metilsulfate (242), cyhalofop-butyl (191 ), trifluralin (791 ), fluthiamide (flufenacet; (362)), isoxaben (466), prosulfocarb (656), triallate (772), 2,4-D (205); benfluamid, cinidon-ethyl (152), flufenpyr, picolinafen (Code No. AC 900001 ; (621 )), propoxycarbazone (Code No. MKH 6561 ; (541)); pretilachlor (632), cinosulfuron (154), fenclorim (325), pyriftalid (Code No. CGA 279 233), metolachlor (529), S-metolachlor (530), mixtures of metolachlor and S-metolachlor, preferably mixtures thereof containing 50-90 %, especially 70-90 % S-metolachlor, bensulfuron-methyl (66), imazosulfuron (444), pyrazosulfuron-ethyl (665), azimsulfuron (45), esprocarb (296), mefenacet (491 ), molinate (542), propanil (644), pyrazolate (pyrazolynate; (663)), fenoxaprop-ethyl ("The Pesticide Manual", Editor C. Tomlin, 10th Edition, British Crop Protection Council, 1994, Entry No. (299)), bispyribac (82), bispyribac-sodium (82), pyriminobac-methyl (676), cafenstrole (108), oxaziclomefone (Code No. MY-100; (583)), dymron (daimuron; (207)), fentrazamide (Code No. NBA 061 ; (340)), indanofan (Code No. MK243; (450)), etobenzanid (Code No. HW-52; (311 )), oxadiargyl (578), halosulfuron-methyl (414), clomazone (159), oxadiazon (579), benzobicyclon (Code No. SAN1315H; (70)), mefenpyr-diethyl (492); profoxydim (Code No. BAS 625H; (54)), pyrazogyl; cyclosulfamuron (186), flazasulfuron (349), flufenacet (362), benfuresate (63), bentazone (69), bromobutide (91 ), dithiopyr (275), ethametsulfuron-methyl (299), flamprop-M (348), methyldymron (521 ), quinclorac (681), thiazopyr (752) and mesosulfuron.
The above herbicidal active ingredients under b) are known and are described, for example, in "The Pesticide Manual", Editor C.D.S. Tomlin, 12th Edition, British Crop Protection Council, 2000 under the Entry Nos. included in brackets; for example, triasulfuron (773) is described therein under Entry No. 773.
The S-enantiomer of glufosinate (406), S-glufosinate, is registered under CAS Reg. No. [35597-44-5].
Metamifop (Dongbu Hannong; Code No. DBH 129) is known as a herbicide and is registered under CAS Reg. No. [256412-89-2].
Fluazolate (Monsanto; Code No. JV-485, MON 48500) is also known as a herbicide under the common name isopropazole and is registered under CAS Reg. No. [174514-07-9].
The compound of formula 2.1 is known as a herbicide under the common name benfluamid (UBE; Code No. UBH 820) and is registered under CAS Reg. No. [113604-08-7].
Flufenpyr is known as a herbicide and is registered under CAS Reg. No. [188489-06-7].
The compound of formula 2.2
is known as a herbicide under the common name pyrazogyl (Aventis; Code No. AEB 172391) and is registered under CAS Reg. No. [158353-15-2].
The compound of formula 2.3
is known as a herbicide under the common name mesosulfuron (Aventis; Code No. AEF 130060) and is registered under CAS Reg. No. [208465-21-8].
Pyriftalid and its preparation are described, for example, in EP-B-0 447 506. The invention also includes the salts that the compounds of formula I having acid hydrogen, especially the derivatives having carboxylic acid groups (e.g. carboxyl-substituted alkyl, alkenyl and alkynyl groups), are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides used as salt formers, emphasis is to be given to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to those of sodium and potassium.
Examples of suitable amines for ammonium salt formation that come into consideration are ammonia as well as primary, secondary and tertiary Cι-C-*8alkylamines, d-dhydroxyalkyl- amines and C2-C alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl- hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl- butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n- amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butyl- ethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2- amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethyl- amine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butyl- amine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxy- anilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
Preferred compounds of formula I are those wherein each R, independently is halogen, -CN, -NO2> -C(R10)=NORn, -ORi3, -SO2R16) -OSO2R17, C C8alkyl or C2-C8alkenyl, or is C C8alkyl mono- or poly-substituted by halogen or by -CN; R 0 is hydrogen or C C4alkyl; and Rn is d-C8alkyl. Preference is given also to those compounds of formula I wherein each R2 independently is halogen, -CN, -NO2, -NR36R37, -CO2R38, -C(R41)=NOR42, -OR-M,
-SO2R47, -OSO-^R^ or d-C8alkyl, or is C C8alkyl mono- or poly-substituted by halogen, -CN or by -CO2R57;
R36 and R37 are hydrogen;
R38 is hydrogen or d-C8alkyl;
R41 is hydrogen or C C4alkyl; and
R42 is d-C8alkyl.
An especially preferred group of compounds of formula I comprises those compounds wherein each R-* independently is halogen, -CN, -NO2, -C(Rι0)=NORn, -OR13, -SO2Ri6,
-OSO2Rι7, d-C8alkyl or C2-C8alkenyl, or is d-C8alkyl mono- or poly-substituted by -CN;
R10 is hydrogen or d-C4alkyl;
Rn is C C8alkyl; each R2 independently is halogen, -CN, -NO2, -NR36R37, -COaRss, -C(R4ι)=NOR42, -OR^,
-SO2R 7, -OSO2R48 or d-C8alkyl, or is d-C8alkyl mono- or poly-substituted by -CN or by
-CO2R57;
R36 and R37 are hydrogen;
R38 is hydrogen or d-C8alkyl;
R41 is hydrogen or Cι-C4alkyl;
R42 is d-C8alkyl; and
R3 and R4 are each independently of the other hydrogen or d-C4alkyl.
Also of interest are compounds of formula I wherein R^ is halogen or -CN, or is d-C8alkyl substituted by -CN, or is Cι-C8alkoxy.
Very special preference is given to those compounds of formula I wherein R2 is halogen, -CN, C*ι-C8alkyl substituted by -CN, or is C C8alkoxy, especially wherein at least one of the substituents R-* or R2 is d-C8alkyl substituted by -CN.
Preference is given also to compounds of formula I wherein n is 0, 1 or 2 and m is 0, 1 , 2, 3 or 4, especially wherein n is 1 or 2 and m is 1 or 2.
Of special interest are compounds of formula I wherein R3 and R4 are hydrogen. ln an outstanding group of compounds of formula I, the group
occupies the 2-position on the pyridine ring, preferably with n being 1 or 2 and Ri occupying the 3- and/or 5-position on the pyridine ring.
Preference is given also to compounds of formula I wherein m is 1 or 2 and R2 occupies the 3-position on the phenyl ring.
Emphasis should be given also to compounds of formula I wherein R-i is hydrogen, fluorine, chlorine, bromine, methoxy, difluoromethoxy, trifluoromethyl or isopropylthio;
R2 is cyanomethyl, chlorine or bromine;
R3 and R are hydrogen; n is 1 or 2 and m is 1.
Preferred synergistic mixtures according to the invention for controlling weeds and grasses in crops of cereals comprise, as co-herbicides under b), compounds selected from the group: triasulfuron, prosulfuron, clodinafop-propargyl, terbutryn, fenoxaprop-P-ethyl, diclof op-methyl, tralkoxydim, butroxydim, amidosulfuron, chlorsulfuron, ethoxysulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, thifensulfuron-methyl, tribenuron-methyl, imazamethabenz-methyl, flucarbazone-sodium, iodosulfuron-methyl- sodium, florasulam, flumetsulam, metosulam, chlortoluron, methabenzthiazuron, bromoxynil, pyridate, bifenox, fluoroglycofen-ethyl, carfentrazone-ethyl, fluazolate, cyhalofop-butyl, azimsulfuron, bensulfuron-methyl, cinosulfuron, cyclosulfamuron, fentrazamide, flazasulfuron, fluazolate, bentazone, ethametsulfuron-methyl, halosulfuron-methyl, quinclorac, imazosulfuron, pyrazosulfuron-ethyl, benfluamid, cinidon-ethyl, flufenpyr, picolinafen and propoxycarbazone.
Preferred synergistic mixtures according to the invention for controlling weeds and grasses in crops of rice comprise, as co-herbicides under b), compounds selected from the group: pretilachlor, cinosulfuron, triasulfuron, fenclorim, pyriftalid, clodinafop-propargyl, metolachlor, S-metolachlor, mixtures of metolachlor and S-metolachlor, preferably mixtures thereof containing 50-90 %, especially 70-90 % S-metolachlor, bensulfuron-methyl, imazosulfuron, pyrazosulfuron-ethyl, metsulfuron-methyl, azimsulfuron, mefenacet, cyhalof op-butyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, cafenstrole, glyphosate, S-glufosinate, glufosinate, sulfosate, halosulfuron-methyl, oxadiazon, mefenpyr-diethyl, indanofan, profoxydim and pyrazogyl.
Further preferred synergistic mixtures according to the invention for controlling weeds and grasses in crops of cereals and rice comprise, as co-herbicides under b), compounds selected from the group: amidosulfuron, azimsulfuron, bensulfuron-methyl, bromoxynil, carfentrazone-ethyl, chlorsulfuron, cinosulfuron, clodinafop-propargyl, cyclosulfamuron, cyhalof op-butyl, dicamba, diclofop-methyl, ethoxysulfuron, fenoxaprop-P-ethyl, flazasulfuron, florasulam, fluazolate, flufenacet, flupyrsulfuron, flupyrsulfuron-methyl-sodium, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron-methyl, benfuresate, bentazone, bromobutide, dithiopyr, ethametsulfuron-methyl, flamprop-M, fluoroglycofen-ethyl, halosulfuron-methyl, mefenacet, methyldymron, pyridate, quinclorac, quinmerac, thiazopyr, tralkoxydim, imazosulfuron, indanofan, MCPA, MCPB, pyrazosulfuron-ethyl and mesosulfuron.
It is extremely surprising that the combination of the compound of formula I with one or more active ingredients selected from the co-herbicides under b) exceeds the additive effect on the weeds to be controlled that is to be expected in principle and thus broadens the range of action of the individual active ingredients especially in two respects: firstly, the rates of application of the individual compounds of formula I and co-herbicides under b) are reduced while a good level of action is maintained and, secondly, the composition according to the invention achieves a high level of weed control also in those cases where the individual substances, in the low rates of application range, have become useless from the agronomic standpoint. The result is a considerable broadening of the spectrum of weeds and an additional increase in selectivity in respect of the crops of useful plants, as is necessary and desirable in the event of an unintentional overdose of active ingredient. The composition according to the invention, while retaining excellent control of weeds in crops of useful plants, also allows greater flexibility in succeeding crops.
The composition according to the invention can be used against a large number of agronomically important weeds, such as Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. The composition according to the invention is suitable for all methods of application conventionally used in agriculture, e.g. pre-emergence application, post-emergence application and seed dressing. The composition according to the invention is suitable especially for controlling weeds in crops of useful plants, such as rape, sugar beet, sugar cane, plantation crops, soybeans and, especially, cereals, rice and maize, and also for non-selective weed control.
"Crops" are to be understood to mean also those crops which have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering.
The composition according to the invention comprises the compound of formula I and the co- herbicides under b) in any mixing ratio, but usually has an excess of one component over the others. Generally, the mixing ratios (ratios by weight) of the compound of formula I and the co-herbicides under b) are from 1 :2000 to 2000:1 , especially from 200:1 to 1 :200.
The rate of application may vary within wide limits and depends on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The active ingredient mixture according to the invention can generally be applied at a rate of from 1 to 5000 g of active ingredient mixture per ha.
The mixtures of the compound of formula I with the co-herbicides under b) may be used in unmodified form, that is to say as obtained in the synthesis. Preferably, however, they are formulated in customary manner, together with the adjuvants conventionally used in formulation technology, such as solvents, solid carriers or surfactants, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or mixtures comprising the compounds of formula I and the co-herbicides under b), and also, where appropriate, one or more solid or liquid formulation adjuvants, are prepared in a manner known per se, e.g. by intimately mixing and/or grinding the active ingredients with the formulation adjuvants, e.g. solvents or solid carriers. In addition, surface-active compounds (surfactants) may also be used in the preparation of the formulations.
Examples of solvents and solid carriers are given, for example, in WO 97/34485, page 6.
Depending on the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485, pages 7 and 8.
Also suitable in the preparation of the herbicidal compositions according to the invention are the surfactants conventionally used in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol l-lll, Chemical Publishing Co., New York, 1980-81.
The herbicidal formulations usually contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture comprising a compound of formula I together with the co-herbicides under b), from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
Whereas commercial products preferably will usually be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. Preferred formulations have especially the following compositions: (% = percent by weight))
Emulsifiable concentrates: active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
Dusts: active ingredient mixture: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient mixture: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %
Wettable powders: active ingredient mixture: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
Granules: active ingredient mixture: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The following Examples illustrate the invention further, but do not limit the invention.
F1. Emulsifiable concentrates a) b) c) d) active ingredient mixture 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 % castor oil polyglycol ether 4 % - 4 % 4 %
(36 mol of ethylene oxide) octylphenol polyglycol ether - 4 % - 2 %
(7-8 mol of ethylene oxide) cyclohexanone - - 10 % 20 % arom. hydrocarbon mixture 85% 78% 55% 16%
Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
F2. Solutions a) b) c) d) active ingredient mixture 5% 10% 50% 90%
1 -methoxy-3-(3-methoxy- propoxy)-propane - 20% 20% - polyethylene glycol MW 400 20% 10% . .
N-methyl-2-pyrrolidone - - 30 % 10 % arom. hydrocarbon mixture 75 % 60 %
The solutions are suitable for use in the form of microdrops.
F3. Wettable powders a) b) c) d) active ingredient mixture 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2% -
(7-8 mol of ethylene oxide) highly dispersed silicic acid 1 % 3% 5% 10% kaolin 88% 62% 35% .
The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration. F4. Coated granules a) b) c) active ingredient mixture 0.1 % 5% 15% highly dispersed silicic acid 0.9 % 2% 2% inorganic carrier 99.0 % 93% 83%
(diameter 0.1 - 1 mm) e.g. CaCO3 or SiO2
The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.
F5. Coated granules a) b) c) active ingredient mixture 0.1 % 5% 15% polyethylene glycol MW 200 1.0 % 2% 3% highly dispersed silicic acid 0.9 % 1 % 2% inorganic carrier 98.0 % 92% 80%
(diameter 0.1 - 1 mm) e.g. CaCO3 or SiO2
The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruder qranules a) b) c) d) active ingredient mixture 0.1 % 3% 5% 15% sodium lignosulfonate 1.5 % 2% 3% 4% carboxymethylcellulose 1.4 % 2% 2% 2% kaolin 97.0 % 93% 90% 79%
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c) active ingredient mixture 0.1 % 1 % 5% talcum 39.9 % 49% 35% kaolin 60.0 % 50% 60%
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill. F8. Suspension concentrates a) b) c) d) active ingredient mixture 3 % 10 % 25 % 50 % ethylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether - 1 % 2 % -
(15 mol of ethylene oxide) sodium lignosulfonate 3 % 3 % 4 % 5 % carboxymethylcellulose 1 % 1 % 1 % 1 %
37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 % water 87 % 79 % 62 % 38 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
It is often more practical for the compound of formula I and the mixing partner or partners under b) to be formulated separately and then to be brought together in the desired mixing ratio in the applicator in the form of a "tank mixture" in water shortly before application.
Biological Examples:
A synergistic effect exists whenever the action of the active ingredient combination of the compound of formula I and co-herbicides under b) is greater than the sum of the actions of the active ingredients applied separately.
The herbicidal action to be expected We for a given combination of two herbicides can be calculated as follows (see COLBY, S.R., "Calculating synergistic and antagonistic response of herbicide combinations", Weeds 15, pages 20-22, 1967):
We = X + [Y* (l00- X)/ l00]
wherein:
X = percentage herbicidal action on treatment with the compound of formula I at a rate of application of p kg per hectare, compared with the untreated control (= 0 %). Y = percentage herbicidal action on treatment with a co-herbicide under b) at a rate of application of q kg per hectare, compared with the untreated control.
We = expected herbicidal action (percentage herbicidal action compared with the untreated control) following treatment with the compound of formula I and co-herbicide under b) at a rate of application of p + q kg of active ingredient per hectare.
When the action actually observed is greater than the value to be expected We, there is a synergistic effect.
The synergistic effect of the combinations of the compound of formula I with the co- herbicides under b) is demonstrated in the following Examples.
Experiment description - pre-emerqence test:
Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots. Directly after sowing, the test compounds are applied in aqueous suspension by spraying (500 litres of water per ha). The rates of application depend on the optimum concentrations determined under field conditions and greenhouse conditions. The test plants are then grown in the greenhouse under optimum conditions. The tests are evaluated after 36 days (% action, 100 % = plant has died, 0 % = no phytotoxic action). The mixtures used in this test exhibit good results.
Experiment description - post-emergence test:
The test plants are grown to the 2- to 3-leaf stage in plastics pots under greenhouse conditions. A standard soil is used as cultivation substrate. At the 2- to 3-leaf stage, the herbicides are applied to the test plants both alone and in admixture. Application is carried out using an aqueous suspension of the test compounds in 500 litres of water per ha. The rates of application depend on the optimum concentrations determined under field conditions and greenhouse conditions. The tests are evaluated after 33 days (% action, 100 % = plant has died, 0 % = no phytotoxic action).
In this test, too, the mixtures used exhibit good results.
It has been shown, surprisingly, that specific safeners are suitable for mixing with the synergistic composition according to the invention. The present invention accordingly relates also to a selectively herbicidal composition for controlling grasses and weeds in crops of useful plants, especially in crops of cereals, rice and maize, that comprises a compound of formula I, one or more compounds selected from the co-herbicides under b), and a safener (counter agent, antidote) that protects the useful plants, but not the weeds, against the phytotoxic action of the herbicide, as well as to the use of such a composition in the control of weeds in crops of useful plants.
There is accordingly also proposed in accordance with the invention a selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of ab) an amount, effective for herbicide synergism, of a compound of formula I and one or more compounds selected from the co-herbicides under b) and c) an amount, effective for herbicide antagonism, of a compound selected from the compound of formula 3.1
and the compound of formula 3.2
and the compound of formula 3.3
(3.3), and its free acid and salts,
C(O)-O-CH(CH3)C5Hι n
and the compound of formula 3.4 (3.4), and its the free acid and salts,
and the compound of formula 3.5
and the compound of formula 3.6
and the compound of formula 3.7
and the compound of formula 3.8
and the compound of formula 3.9
CI2CHCON(CH2CH=CH2)2 (3.9), and the compound of formula 3.10 and the compound of formula 3.11
and the compound of formula 3.12
(3.12), and its ethyl ester,
and the compound of formula 3.13
and the compound of formula 3.14
and the compound of formula 3.15 (3.15)
and the compound of formula 3.16
C2H5
The compounds of formulae 3.1 to 3.16 are known and are described, for example, in the "Pesticide Manual", 12th Edition, British Crop Protection Council, 2000 under the entry numbers 65 (formula 3.1 , benoxacor), 325 (formula 3.2, fenclorim), 163 (formula 3.3, cloquintocet-mexyl), 492 (formula 3.4, mefenpyr-diethyl), 401 (formula 3.5, furilazole), 389 (formula 3.8, fluxofenim), 225 (formula 3.9, dichlormid) and 376 (formula 3.10, flurazole). The compound of formula 3.11 is known under the designation MON 4660 (Monsanto) and is described, for example, in EP-A-0 436 483.
The free acid and salts of cloquintocet-mexyl (formula 3.3) are known, for example, from WO 02/34048, and the free acid and salts of mefenpyr-diethyl (formula 3.4) are known, for example, from WO 01/17353.
The compound of formula 3.6 (AC 304415) is described, for example, in EP-A-0 613 618, and the compound of formula 3.7 in DE-A-29 48 535. The compounds of formula 3.12 are known under the common names isoxadifen and isoxadifen-ethyl, are described in DE-A-43 31 448 and are registered under the CAS Reg. Nos. [209866-92-2] and [163520- 33-0], and the compound of formula 3.13 is described in DE-A-35 25 205. The compound of formula 3.14 is known, for example, from US-A-5 215 570, and the compound of formula 3.15 from EP-A-0 929 543. The compound of formula 3.16 is described in WO 99/00020. In addition to the compound of formula 3.16, the other 3-(5-tetrazolyl- carbonyl)-2-quinolones described in WO 99/00020, especially the compounds specifically disclosed in Tables 1 and 2 on pages 21 to 29, are also suitable for protecting crop plants against the phytotoxic action of the compounds of formula I.
The invention relates also to a selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) a herbicidally effective amount of a compound of formula I and c) an amount, effective for herbicide antagonism, of a compound selected from the compounds of formulae 3.1 , 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.10, 3.11 , 3.12, 3.13, 3.14,
3.15 and 3.16.
Preferred mixtures according to the invention comprise as safener a compound selected from the compounds of formulae 3.1 , 3.3 and 3.8. Such safe/iers are suitable especially for those compositions according to the invention that comprise the above-mentioned preferred co-herbicides under b).
Combinations of the compound of formula I with the compound of formula 3.3 have been found to be very especially effective compositions. Such a composition is preferably used together with clodinafop-propargyl (156).
The invention relates also to a method for the selective control of weeds in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with a herbicidally effective amount of a herbicide of formula I, optionally one or more herbicides selected from the co-herbicides under b), and an amount, effective for herbicide antagonism, of a safener from formulae 3.1 to 3.16.
As crop plants that can be protected by the safeners of formulae 3.1 to 3.16 against the damaging effect of the above-mentioned herbicides there come into consideration especially cotton, soybeans, sugar beet, sugar cane, plantation crops, rape and, very especially, cereals, rice and maize. "Crops" are to be understood to mean also those crops which have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering. The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, such as, for example Stellaria, Agrostis, Digitaria, Avena, Apera, Brachiaria, Phalaris, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Panicum, Bromus, Alopecurus, Sorghum halepense, Sorghum bicolor, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
Areas of cultivation include the areas of ground on which the crop plants are already growing or which have been sown with the seed material of those crop plants, as well as ground intended for the cultivation of such crop plants.
Depending on the intended use, a safener of formula 3.1 to 3.16 can be used in the pretreatment of the seed material of the crop plant (dressing of the seeds or cuttings) or can be introduced into the soil before or after sowing. It can, however, also be applied, either alone (so-called "split application") or together with the herbicide, after emergence of the plants. The treatment of the plants or seeds with the safener can therefore in principle be carried out independently of the time at which the herbicide is applied but implies a period of time in which herbicide and safener are still able to meet in order that the safening action can subsequently come about at all. So-called "split application" must be distinguished from separate application. The plants can, however, also be treated by simultaneous application of herbicide and safener (e.g. in the form of a tank mixture). The ratio of the rate of application of safener to the rate of application of herbicide depends largely on the method of application. In the case of field treatment, which is carried out either using a tank mixture comprising a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of herbicides to safener is generally from 100:1 to 1 :10, preferably from 20:1 to 1 :1. In the case of field treatment it is usual to apply from 0.001 to 1.0 kg of safener per ha, preferably from 0.001 to 0.25 kg of safener per ha.
The rate of application of herbicides is generally from 0.001 to 2 kg per ha, but preferably from 0.005 to 0.5 kg per ha.
The compositions according to the invention are suitable for all methods of application conventionally used in agriculture, e.g. pre-emergence application, post-emergence application and seed dressing. In the case of seed dressing, generally from 0.001 to 10 g of safener per kg of seed, preferably from 0.05 to 2 g of safener per kg of seed, are applied. When the safener is applied in liquid form shortly before sowing, with soaking of the seeds, then advantageously the safener solutions used contain the active ingredient in a concentration of from 1 to 10 000 ppm, preferably from 100 to 1000 ppm.
For the purpose of application, the safeners of formulae 3.1 to 3.16 or combinations of those safeners with a herbicide of formula I and optionally one or more herbicides selected from the co-herbicides under b) are advantageously formulated together with adjuvants customary in formulation technology, e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
Such formulations are described, for example, in WO 97/34485, pages 9 to 13. The formulations are prepared in known manner, e.g. by intimately mixing and/or grinding the active ingredients with liquid or solid formulation adjuvants, e.g. solvents or solid carriers. In addition, surface-active compounds (surfactants) can also be used in the preparation of the formulations. Solvents and solid carriers suitable for that purpose are mentioned, for example, in WO 97/34485, on page 6.
Depending on the nature of the compound of formula I, the co-herbicides under b) and the safeners of formulae 3.1 to 3.16 to be formulated, there come into consideration as surface- active compounds non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8. Also suitable for the preparation of the herbicidal compositions according to the invention are the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol. Nil, Chemical Publishing Co., New York, 1980-81. The herbicidal formulations usually contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture comprising a compound of formula I, a compound selected from the co-herbicides under b) and the safeners of formulae 3.1 to 3.16, from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products preferably will usually be formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. For the use of safeners of formulae 3.1 to 3.16, or of compositions comprising them, in the protection of crop plants against the damaging effects of herbicides of formula I and co-herbicides under b), various methods and techniques come into consideration, such as, for example, the following:
0 Seed dressing a) Dressing of the seeds with a wettable powder formulation of a compound from formulae 3.1 to 3.16 by shaking in a vessel until uniformly distributed over the seed surface (dry dressing). In that procedure approximately from 1 to 500 g of a compound from formulae 3.1 to 3.16 (4 g to 2 kg of wettable powder) are used per 100 kg of seed material. b) Dressing of the seeds with an emulsifiable concentrate of a compound from formulae 3.1 to 3.16 according to method a) (wet dressing). c) Dressing by immersing the seed material for from 1 to 72 hours in a liquor comprising from 100 to 1000 ppm of a compound from formulae 3.1 to 3.16 and optionally subsequently drying the seeds (immersion dressing).
Dressing the seed material or treating the germinated seedling are naturally the preferred methods of application, because treatment with the active ingredients is directed entirely at the target crop. Generally from 1 to 1000 g of antidote, preferably from 5 to 250 g of antidote, are used per 100 kg of seed material, but depending on the methodology, which also allows other active ingredients or micronutrients to be added, concentrations above or below the limits indicated may be employed (repeat dressing). ii) Application as a tank mixture
A liquid formulation of a mixture of antidote and herbicide is used (ratio by weight of the one to the other from 10:1 to 1 :100), the rate of application of herbicide being from 0.005 to
5.0 kg per hectare. Such tank mixtures are applied before or after sowing. iii) Application to the seed furrow
The compound from formulae 3.1 to 3.16 is introduced into the open, sown seed furrow in the form of an emulsifiable concentrate, wettable powder or granules. Once the seed furrow has been covered over, the herbicide is applied in the usual manner pre-emergence. iv) Controlled release of active ingredient
The compound from formulae 3.1 to 3.16 is applied in solution to mineral carrier granules or polymerised granules (urea/formaldehyde) and dried. If desired, it is also possible to apply a coating that allows the active ingredient to be released in metered amounts over a specific period of time (coated granules).
Preferred formulations have especially the following compositions:
(% = percent by weight)
Emulsifiable concentrates: active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
Dusts: active ingredient mixture: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient mixture: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %
Wettable powders: active ingredient mixture: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 % Granules: active ingredient mixture: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The following Examples illustrate the invention further, but do not limit the invention.
Formulation Examples for mixtures of herbicides of formula I, optionally of co-herbicides b). and safeners of formulae 3.1 to 3.16 (% = percent by weight)
F1. Emulsifiable concentrates a) b) c) d) active ingredient mixture 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 6 %% 8 % 6 % 8 % castor oil polyglycol ether 4 % . 4 % 4 %
(36 mol of ethylene oxide) octylphenol polyglycol ether - 4 % - 2 %
(7-8 mol of ethylene oxide) cyclohexanone - - 10 % 20 % o arom. hydrocarbon mixture 85 % 78 % 55 % 16 %
Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
F2. Solutions a) b) c) d) active ingredient mixture 5 % 10 % 50 % 90 %
1 -methoxy-3-(3-methoxy- propoxy)-propane - 20 % 20 % - polyethylene glycol MW 400 20 % 10 % - -
N-methyl-2-pyrrolidone - - 30 % 10 % arom. hydrocarbon mixture 75 % 60 % - -
The solutions are suitable for use in the form of microdrops. F3. Wettable powders a) b) c) d) active ingredient mixture 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2% -
(7-8 mol of ethylene oxide) highly dispersed silicic acid 1 % 3% 5% 10% kaolin 88% 62% 35% _
The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
F4. Coated granules a) b) c) active ingredient mixture 0.1 % 5% 15% highly dispersed silicic acid 0.9 % 2% 2% inorganic carrier 99.0 % 93% 83%
(diameter 0.1 -1 mm) e.g. CaCO3 or SiO2
The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.
F5. Coated granules a) b) c) active ingredient mixture 0.1 % 5% 15% polyethylene glycol MW 200 1.0% 2% 3% highly dispersed silicic acid 0.9 % 1 % 2 % inorganic carrier 98.0 % 92 % 80 %
(diameter 0.1 - 1 mm) e.g. CaCO3 or SiO2
The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. F6. Extruder granules a) b) c) d) active ingredient mixture 0.1 % 3% 5% 15% sodium lignosulfonate 1.5 % 2% 3% 4% carboxymethylcellulose 1.4 % 2% 2% 2% kaolin 97.0 % 93% 90% 79%
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c) active ingredient mixture 0.1 % 1 % 5% talcum 39.9 % 49% 35% kaolin 60.0 % 50% 60%
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d) active ingredient mixture 3% 10% 25% 50% ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether - 1 % 2% -
(15 mol of ethylene oxide) sodium lignosulfonate 3% 3% 4% 5% carboxymethylcellulose 1 % 1 % 1 % 1 %
37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 % water 87% 79% 62% 38%
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
It is often more practical for the compounds of formula I, co-herbicides under b) and the safeners of formulae 3.1 to 3.16 to be formulated separately and then to be brought together in the desired mixing ratio in the applicator in the form of a "tank mixture" in water shortly before application. The ability of the safeners of formulae 3.1 to 3.16 to protect crop plants against the phytotoxic action of herbicides of formula I is illustrated in the following Examples.
Biological Example: Safeninq action
The test plants are grown in plastics pots under greenhouse conditions to the 4-leaf stage. At that stage, either the herbicides alone or the mixtures of the herbicides with the test compounds being tested as safeners are applied to the test plants. The test compounds are applied in the form of an aqueous suspension prepared from a 25 % wettable powder (Example F3, b)), using 500 litres of water per ha. 4 weeks after application, the phytotoxic action of the herbicides on the crop plants, e.g. maize and cereals, is evaluated using a percentage scale. 100 % indicates that the test plant has died, 0 % indicates no phytotoxic action. The mixtures according to the invention exhibit a good action in this test.

Claims

What is claimed is:
1. A selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, comprises as active ingredient a mixture of
a) a herbicidally effective amount of a compound of formula
wherein n is O, 1 , 2, 3 or 4; each Ri independently is halogen, -CN, -SCN, -SF5, -NO2) -NR5R6, -CO2R7, -CONR8R9, -C(Rio)=NORn, -COR12, -OR-13, -SR14, -SORι5, -SO2Rι6, -OSO2Rι7, C C8alkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl; or is d-C8alkyl, C2-C8alkenyl or C2-C8alkynyl mono- or poly- substituted by halogen, -CN, -NO2, -NR18Rι9, -CO2R20, -CONR2iR22> -COR23, -C(R24)=NOR25, -C(S)NR26R27, -C(Cι-C4alkylthio)=NR28, -OR29, -SR30, -SOR31, -SO2R32 or by C3-C6cycloalkyl; or each Ri is C3-C6cycloalkyl mono- or poly-substituted by halogen, -CN, -NO2, -NRι8Rι9, -CO2R20, -CONR2ιR22, -COR23, -C(R24)=NOR25, -C(S)NR26R27, -C(Cι-C4alkylthio)=NR28, - SR30, -SOR31, -SO2R32 or by C3-C6cycloalkyl; or each Ri independently is phenyl, which may in turn be mono- or poly-substituted by halogen, d-dalkyl, CrC4haloalkyl, C C4alkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or by d-C4alkylsulfonyl; or two adjacent Ri substituents together form a d-C7alkylene bridge which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C6alkyl, the total number of ring atoms being at least 5 and at most 9; or two adjacent Ri substituents together form a C2-C7alkenylene bridge which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C6alkyl, the total number of ring atoms being at least 5 and at most 9; R3 and R4 are each independently of the other hydrogen, halogen, -CN, Cι-C4alkyl or d-C4alkoxy; or
R3 and R4 together are C2-C5alkylene; R5 is hydrogen or C C8alkyl; R6 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl; it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, Cι-C4alkylthio, C1-C4alkylsulfinyl or by Cι-C4alkylsulfonyl; or R5 and R6 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R7 is hydrogen, CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- or poly-substituted by halogen, d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, d-C4alkylthio, d-C4alkylsulfinyl or by d-C4alkylsulfonyl; R8 is hydrogen or d-C8alkyl;
R9 is hydrogen or d-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by COOH, C C8- alkoxycarbonyl or by -CN, or
Rg is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-dalkyl, d-C4haloalkyl, C C4alkoxy, -CN, -NO2, C C4alkylthio, Cι-C4alkylsulfinyl or by C C4alkylsulfonyl; or R8 and Rg together are C2-C5alkylene; R10 is hydrogen, d-C alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R11 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; R12 is hydrogen, d-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; R13 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl; or
R13 is phenyl or phenyl-Cι-C6alkyl, it being possible for the phenyl ring in turn to be mono- or poly-substituted by halogen, Crdalkyl, d-C haloalkyl, d-dalkoxy, -CN, -NO2 or by -S(O)2Cι-C8alkyl, or
R13 is d-C8alkyl mono- or poly-substituted by halogen, -CN or by d-C4alkoxy; Rι4 is hydrogen, CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is Cι-C8alkyl mono- or poly- substituted by halogen, -CN or by d-C alkoxy;
R15. ie and R17 are each independently of the others C C8alkyl, C3-C8alkenyl or C3-C8- alkynyl, or Cι-C8alkyl mono- or poly-substituted by halogen, -CN or by C -C4alkoxy; Rι8 is hydrogen or Cι-C8alkyl;
Rι9 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, Cι-C4alkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2) C C4alkylthio, Cι-C4alkylsulfinyl or by d-C4alkylsulfonyl; or Rι8 and Ri9 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom; R20 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or by Cι-C4alkylsulfonyl; R21 is hydrogen or Cι-C8alkyl;
R22 is hydrogen or Cι-C8alkyl, or is C C8alkyl mono- or poly-substituted by COOH, d-C8- alkoxycarbonyl or by -CN, or
R22 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, C C haloalkyl, d-C4alkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by d-C4alkylsulfonyl; or R2ι and R22 together are C2-C5alkylene; R23 is hydrogen, C C4alkyl, d-C haloalkyl or C3-C6cycloalkyl; R24 is hydrogen, Cι-C4alkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R25 is hydrogen, Cι-C8alkyl, C3-C8alkenyl , C3-C8alkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl; R26 is hydrogen or Cι-C8alkyl;
R27 is hydrogen or d-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by COOH, d-C8- alkoxycarbonyl or by -CN, or
R27 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, Cι-C4alkyl, d-C haloalkyl, d-C4alkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by Cι-C4alkylsulfonyl; or R26 and R2 together are C2-C5alkylene; R28 is hydrogen or Cι-C8alkyl;
R∞ and R30 are each independently of the other hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono- or poly-substituted by halogen, -CN or by d-C4alkoxy; R31 and R32 are each independently of the other Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or CrC8alkyl mono- or poly-substituted by halogen, -CN or by d-C4alkoxy; m is O, 1 , 2, 3, 4 or 5; each R2 independently is halogen, -CN, -SCN, -SF5, -NO2> -NR36R3 > -CO2R38, -CONR39R40l -C(R4ι)=NOR42, -COR43, -OR44, -SR^, -SOR46, -SO2R47, OSO^ -N([CO]pR49)COR5o, -N(OR5ι)COR52, -N(R53)CO2R54 or -N-phthalimide; R36 is hydrogen or d-C8alkyl; and
R37 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C alkyl, d-dhaloalkyl, d-dalkoxy, -CN, -NO2, Cι-C4alkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; or R36 and R37 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R38 is hydrogen, C C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is C-*-C8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- or poly-substituted by halogen, Cι-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, Cι-C halo- alkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C1-C4alkylsulfinyl or by Cι-C4alkylsulfonyl; R39 is hydrogen or Cι-C8alkyl;
R^ is hydrogen or d-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by -COOH, C C8- alkoxycarbonyl or by -CN, or
R4o is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-C haloalkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfinyl or by d-C4alkylsulfonyl; or R39 and R 0 together are C3-C5alkylene; R4ι is hydrogen, d-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R42 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; R^ is hydrogen, d-dalkyl, d-C haloalkyl or C3-C6cycloalkyl; R , is hydrogen, CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl; or
R^ is phenyl or phenyl-d-C6alkyl, it being possible for the phenyl ring in turn to be mono- or poly-substituted by halogen, d-C alkyl, d-C4haloalkyl, Cι-C alkoxy, -CN, -NO2 or by -S(O)2Cι-C8alkyl, or
R^ is d-C8alkyl mono- or poly-substituted by halogen, -CN or by Cι-C4alkoxy; R^ is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-C8alkyl mono- or poly- substituted by halogen, -CN or by Cι-C4alkoxy;
R4e. R47 and R^ are each independently of the others C C8alkyl, C3-C8alkenyl or C3-C8- alkynyl, or d-C8alkyl mono- or poly-substituted by halogen, -CN or by d-C4alkoxy; p is 0 or 1 ;
R4g. R50, R51. R52. R53 and R*^ are each independently of the others hydrogen, C C8alkyl, or phenyl which may in turn be mono- or poly-substituted by halogen, d-C8alkyl, d-dhaloalkyl, d-C4alkoxy, -CN, -NO2> d-C8alkylthio, C C8alkylsulfinyl or by d-C8alkylsulfonyl; or each R2 independently is C C8alkyl, or is d-C8alkyl mono- or poly-substituted by halogen, -CN, -NO2, -NR55R56, -CO2R57, -CONR58R59, -COR60, -C(R61)=NOR62, -C(S)NR63R64, -C(Cι-C4alkylthio)=NR65, -ORee, -SR67, -SOR68> -SO2R69, -O(SO2)R70, -N(R7ι)CO2R72, -N(R73)COR74 or by C3-C6cycloalkyl; or each R2 independently is C2-C8alkenyl, or is C2-C8alkenyl mono- or poly-substituted by -CN, -NO2, -CO2R75, -CONR76R77, -COR78, -C(R79)=NOR80, -C(S)NR81R82, -C(C1-C4alkylthio)=NR83 or by C3-C6cycloalkyl; or each R2 independently is C2-C8alkynyl, or is C2-C8alkynyl mono- or poly-substituted by halogen, -CN, -COsR-^, -CONR85R86, -COR87) -C(R88)=NOR89, -C(S)NR90R9ι, -C(C C4alkylthio)=NR92 or by C3-C6cycloalkyl; or each R2 independently is C3-C6cycloalkyl, or is C3-C6cycloalkyl mono- or poly-substituted by halogen, -CN, -CO2R93, -CONR94R95, -COR96, -C(R97)=NOR98, -C(S)NR99Rιoo or by -C(C1-C4alkylthio)=NRιoι; or two adjacent R2 substituents together form a d-C7alkylene bridge which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C6alkyl, the total number of ring atoms being at least 5 and at most 9; or two adjacent R2 substituents together form a C2-C7alkenylene bridge which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C6alkyl, the total number of ring atoms being at least 5 and at most 9; R55 is hydrogen or Cι-C8alkyl;
R56 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, Cι-C4halo- alkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C1-C4alkylsulfinyl or by Cι-C4alkylsulfonyl; or R55 and R56 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R57 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or is d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- or poly-substituted by halogen, d-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-dhaloalkyl, d-C4alkoxy, -CN, -NO2, C C4alkylthio, Cι-C4alkylsulfinyl or by d-C4alkylsulfonyl; R58 is hydrogen or Cι-C8alkyl;
R59 is hydrogen or Cι-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by -COOH, C C8- alkoxycarbonyl or by -CN; or
R59 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C alkyl, d-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; or Rse and R59 together are C2-C5alkylene; R60 is hydrogen, Cι-C alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; R6ι is hydrogen, Cι-C4alkyl, d-C4haloalkyl or C3-C6cycloalkyl; R62 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; and
R63 is hydrogen or Cι-C8alkyl;
Rfw is hydrogen or C C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by -COOH, Ci-Cs- alkoxycarbonyl or by -CN; or
R64 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-C4haloalkyl, d-C4alkoxy,
-CN, -NO2, d-dalkylthio, Cι-C4alkylsulfinyl or by C C4alkylsulfonyl; or
R63 and R*^ together are C2-C5alkylene;
R65 is hydrogen or d-C8alkyl;
R66 and R67 are each independently of the other hydrogen, Cι-C8alkyl, C3-C8alkenyl,
C3-C8alkynyl, or CrC8alkyl mono- or poly-substituted by halogen, -CN or by C C4alkoxy;
Rβa Reg and R70 are each independently of the other Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl mono- or poly-substituted by halogen, -CN or by Cι-C4alkoxy;
R7ι and R73 are each independently of the other hydrogen, d-C8alkyl or Cι-C8alkoxy;
R72 is Cι-C8alkyl;
R74 is hydrogen or d-C8alkyl;
R75 is hydrogen, or is Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- or poly-substituted by halogen, Cι-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, C C4alkyl, d-C4haloalkyl, Cι-C alkoxy, -CN,
-NO2, d-dalkylthio, Cι-C4alkylsulfinyl or by C C4alkylsulfonyl;
R76 is hydrogen or C C8alkyl; -π is hydrogen or d-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by -COOH, Cι-C8- alkoxycarbonyl or by -CN; or
R77 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-dalkyl, d-C4haloalkyl, d-C alkoxy,
-CN, -NO2, d-dalkylthio, d-C4alkylsulfinyl or by C C4alkylsulfonyl; or
R76 and R77 together are C2-C5alkylene;
R78 and R79 are each independently of the other hydrogen, d-C4alkyl, d-C4haloalkyl or
C3-C6cycloalkyl;
R80 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl;
R8ι is hydrogen or Cι-C8alkyl;
R82 is hydrogen or Cι-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by -COOH, Cι-C8- alkoxycarbonyl or by -CN; or R82 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, Cι-C4alkyl, Cι-C4haloalkyl, d-C4alkoxy,
-CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by Cι-C4alkylsulfonyl; or
R8 and R82 together are C2-C5alkylene;
R83 is hydrogen or Cι-C8alkyl;
R&4 is hydrogen, or is C C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- or poly-substituted by halogen, d-C alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, Cι-C4haloalkyl, Cι-C4alkoxy, -CN,
-NO2, Cι-C4alkylthio, d-C4alkylsulfinyl or by C C4alkylsulfonyl;
R85 is hydrogen or Cι-C8alkyl;
R86 is hydrogen or d-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by -COOH, d-C8- alkoxycarbonyl or by -CN; or
R86 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, Cι-C haloalkyl, d-C4alkoxy,
-CN, -NO2, d-dalkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; or
R85 and R86 together are C2-C5alkylene;
R87 is hydrogen, Cι-C4alkyl, Cι-C haloalkyl or C3-C6cycloalkyl;
R88 is hydrogen, d-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R89 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C haloalkyl or C3-C6haloalkenyl;
Rgo is hydrogen or d-C8alkyl;
R9ι is hydrogen or Cι-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by -COOH, d-C8- alkoxycarbonyl or by -CN; or
R91 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-C4haloalkyl, d-C4alkoxy,
-CN, -NO2, d-dalkylthio, d-dalkylsulfinyl or by Cι-C4alkylsulfonyl; or
R9o and Rgi together are C2-C5alkylene;
R92 is hydrogen or d-C8alkyl;
R93 is hydrogen, or is d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which may be mono- or poly-substituted by halogen, Cι-C4alkoxy or by phenyl, it being possible for phenyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, C C4haloalkyl, d-C4alkoxy, -CN,
-NO2) Cι-C4alkylthio, d-C4alkylsulfinyl or by C C4alkylsulfonyl;
R9 is hydrogen or d-C8alkyl;
R95 is hydrogen or Cι-C8alkyl, or is Cι-C8alkyl mono- or poly-substituted by -COOH, Cι-C8- alkoxycarbonyl or by -CN; or R95 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, C C4alkyl, d-C4haloalkyl, C C4alkoxy,
-CN, -NO2, d-C4alkylthio, Cι-C4alkylsulfinyl or by C C4alkylsulfonyl; or
R94 and R95 together are C2-C5alkylene;
R96 is hydrogen, d-dalkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R97 is hydrogen, CrC4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R98 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, d-C haloalkyl or C3-C6haloalkenyl;
R99 is hydrogen or d-Cβalkyl;
R100 is hydrogen or d-C8alkyl, or is CrC8alkyl mono- or poly-substituted by -COOH, C C8- alkoxycarbonyl or by -CN; or
R100 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- or poly-substituted by halogen, d-C4alkyl, d-dhaloalkyl, d-C4alkoxy,
-CN, -NO2, Cι-C4alkylthio, C C4alkylsulfinyl or by C C4alkylsulfonyl; or
Rg9 and R100 together are C2-C5alkylene; and
R10ι is hydrogen or C C8alkyl, or an agrochemically acceptable salt or any stereoisomer or tautomer of a compound of formula I, and
b) a synergistically effective amount of one or more compounds selected from the group consisting of the co-herbicides: triasulfuron (773), prosulfuron (657), clodinafop-propargyl (156), terbutryn (740), dicamba (222), fenoxaprop-P-ethyl (331 ), metamifop, diclofop-methyl (232), tralkoxydim (767), butroxydim (104), amidosulfuron (24), chlorsulfuron (146), ethoxysulfuron (307), flupyrsulfuron (374), flupyrsulfuron-methyl-sodium (374), metsulfuron-methyl (536), sulfosulfuron (714), thifensulfuron-methyl (754), tribenuron-methyl (778), imazamethabenz- methyl (438), flucarbazone-sodium (357), iodosulfuron-methyl-sodium (454), florasulam (351 ), flumetsulam (366), metosulam (533), chlorotoluron (142), isoproturon (464), methabenzthiazuron (510), bromoxynil (93), ioxynil (455), pyridate (672), bifenox (75), fluoroglycofen-ethyl (371 ), carfentrazone-ethyl (1 19), fluazolate (355), diflufenican (245), flurtamone (382), glyphosate (407), sulfosate (407), glufosinate (406), S-glufosinate, bialaphos (bilanafos; (77)), ethalfluralin (298), pendimethalin (599), 2,4-DB (211), dichlorprop (2,4-DP; (228)), MCPA (485), MCPB (487), mecoprop (MCPP; (489)), mecoprop-P (490), clopyralid (162), fluroxypyr (380), quinmerac (682), benazolin-ethyl (59), difenzoquat metilsulfate (242), cyhalofop-butyl (191 ), trifluralin (791 ), fluthiamide (flufenacet; (362)), isoxaben (466), prosulfocarb (656), triallate (772), 2,4-D (205); benfluamid, cinidon-ethyl (152), flufenpyr, picolinafen (Code No. AC 900001 ; (621 )), propoxycarbazone (Code No. MKH 6561 ; (541 )); pretilachlor (632), cinosulfuron (154), fenclorim (325), pyriftalid (Code No. CGA 279 233), metolachlor (529), S-metolachlor (530), mixtures of metolachlor and S-metolachlor, preferably mixtures thereof containing 50-90 %, especially 70-90 % S-metolachlor, bensulfuron-methyl (66), imazosulfuron (444), pyrazosulfuron-ethyl (665), azimsulfuron (45), esprocarb (296), mefenacet (491 ), molinate (542), propanil (644), pyrazolate (pyrazolynate; (663)), fenoxaprop-ethyl ("The Pesticide Manual", Editor C. Tomlin, 10th Edition, British Crop Protection Council, 1994, Entry No. (299)), bispyribac (82), bispyribac-sodium (82), pyriminobac-methyl (676), cafenstrole (108), oxaziclomefone (Code No. MY-100; (583)), dymron (daimuron; (207)), fentrazamide (Code No. NBA 061 ; (340)), indanofan (Code No. MK243; (450)), etobenzanid (Code No. HW-52; (31 1 )), oxadiargyl (578), halosulfuron-methyl (414), clomazone (159), oxadiazon (579), benzobicyclon (Code No. SAN1315H; (70)), mefenpyr-diethyl (492); profoxydim (Code No. BAS 625H; (54)), pyrazogyl; cyclosulfamuron (186), flazasulfuron (349), flufenacet (362), benfuresate (63), bentazone (69), bromobutide (91 ), dithiopyr (275), ethametsulfuron-methyl (299), flamprop-M (348), methyldymron (521 ), quinclorac (681 ), thiazopyr (752) and mesosulfuron.
2. A method of controlling undesired plant growth in a crop of useful plants, which comprises allowing a herbicidally effective amount of a composition according to claim 1 to act on the crop plant or the area of cultivation thereof.
3. A method according to claim 2, wherein the crop plant is a cereal, rice or maize.
4. A method according to claim 2, wherein the crop of useful plants is treated with the said composition at a rate of application corresponding to a total amount of active ingredient of from 1 to 5000 g per hectare.
5. A selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of ab) an amount, effective for herbicide synergism, of a compound of formula I according to claim 1 and one or more compounds selected from the co-herbicides under b) according to claim 1 , and c) an amount, effective for herbicide antagonism, of a compound selected from the compound of formula 3.1
and the compound of formula 3.2
and the compound of formula 3.3
(3.3), and its free acid and salts,
2-C(O)-O-CH(CH3)C5H11-n
and the compound of formula 3.4
(3.4), and its free acid and salts,
and the compound of formula 3.5
and the compound of formula 3.6
and the compound of formula 3.7
and the compound of formula 3.8
and the compound of formula 3.9
CI2CHCON(CH2CH=CH2)2 (3.9), and the compound of formula 3.10
and the compound of formula 3.11 and the compound of formula 3.12
(3.12), and its ethyl ester,
and the compound of formula 3.13
and the compound of formula 3.14
and the compound of formula 3.15
(3.15),
and the compound of formula 3.16 C2H5
6. A method for the selective control of weeds and grasses in a crop of useful plants, which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with an amount, effective for herbicide synergism, of a composition according to claim 5.
7. A method according to claim 6, wherein the rate of application of herbicides is from 1 to 5000 g per ha and the rate of application of safener is from 0.001 to 0.5 kg per ha.
8. A method according to claim 6, wherein the crop of useful plants is a cereal, rice or maize.
9. A selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) a herbicidally effective amount of a compound of formula I according to claim 1 and c) an amount, effective for herbicide antagonism, of a compound selected from the compound of formula 3.1
and the compound of formula 3.2
and the compound of formula 3.3 (3.3), and its free acid and salts,
2-C(O)-O-CH(CH3)C5Hι n
and the compound of formula 3.4
(3.4), and its free acid and salts,
and the compound of formula 3.5
and the compound of formula 3.6
and the compound of formula 3.7
and the compound of formula 3.8 and the compound of formula 3.9
CI2CHCON(CH2CH=CH2)2 (3.9), and the compound of formula 3.10
and the compound of formula 3.11
and the compound of formula 3.12
(3.12), and its ethyl ester,
and the compound of formula 3.13
and the compound of formula 3.14 and the compound of formula 3.15
(3.15),
and the compound of formula 3.16
C2H5
10. A method for the selective control of weeds and grasses in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with an amount, effective for herbicide synergism, of a composition according to claim 9.
EP03720414A 2002-04-03 2003-04-02 Herbicidal composition comprising phenylpropynyloxypyridine compounds Withdrawn EP1492405A1 (en)

Applications Claiming Priority (3)

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CH5592002 2002-04-03
CH559022002 2002-04-03
PCT/EP2003/003471 WO2003082012A1 (en) 2002-04-03 2003-04-02 Herbicidal composition comprising phenylpropynyloxypyridine compounds

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CN112335669A (en) * 2020-10-29 2021-02-09 安徽众邦生物工程有限公司 Weeding composition containing oxaziclomefone and clethodim

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KR20080052606A (en) 2005-08-24 2008-06-11 파이어니어 하이 부렛드 인터내쇼날 인코포레이팃드 Compositions providing tolerance to multiple herbicides and methods of use thereof
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CN112335669A (en) * 2020-10-29 2021-02-09 安徽众邦生物工程有限公司 Weeding composition containing oxaziclomefone and clethodim
CN112335660A (en) * 2020-11-03 2021-02-09 安徽众邦生物工程有限公司 Topramezone and fluroxypyr weeding composition

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AU2003224032A1 (en) 2003-10-13
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WO2003082012A1 (en) 2003-10-09
US20050227871A1 (en) 2005-10-13

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